EP0834502A2 - Polymeric polyionic compounds, process for their preparation and their use as photoinitiators - Google Patents
Polymeric polyionic compounds, process for their preparation and their use as photoinitiators Download PDFInfo
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- EP0834502A2 EP0834502A2 EP97402311A EP97402311A EP0834502A2 EP 0834502 A2 EP0834502 A2 EP 0834502A2 EP 97402311 A EP97402311 A EP 97402311A EP 97402311 A EP97402311 A EP 97402311A EP 0834502 A2 EP0834502 A2 EP 0834502A2
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- European Patent Office
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- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 88
- 238000000034 method Methods 0.000 title claims description 37
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
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- 125000002524 organometallic group Chemical group 0.000 claims abstract description 7
- 239000012954 diazonium Substances 0.000 claims abstract description 6
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- 125000005410 aryl sulfonium group Chemical group 0.000 claims abstract description 5
- -1 organometallic cations Chemical class 0.000 claims description 79
- 125000004432 carbon atom Chemical group C* 0.000 claims description 78
- 239000000178 monomer Substances 0.000 claims description 48
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- 230000005855 radiation Effects 0.000 claims description 37
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- 125000003118 aryl group Chemical group 0.000 claims description 36
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
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- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
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- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
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- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 2
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
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- 150000004294 cyclic thioethers Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
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- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 241000168254 Siro Species 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- XTXNWQHMMMPKKO-UHFFFAOYSA-N tert-butyl 2-phenylethenyl carbonate Chemical compound CC(C)(C)OC(=O)OC=CC1=CC=CC=C1 XTXNWQHMMMPKKO-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- UTLXUGOVTIJBAP-UHFFFAOYSA-N cyclopenta-1,3-diene 5-(2-cyclopenta-2,4-dien-1-ylethyl)cyclopenta-1,3-diene iron(2+) Chemical compound [Fe++].[Fe++].c1cc[cH-]c1.c1cc[cH-]c1.C(C[c-]1cccc1)[c-]1cccc1 UTLXUGOVTIJBAP-UHFFFAOYSA-N 0.000 description 1
- VGBAECKRTWHKHC-UHFFFAOYSA-N cyclopenta-1,3-diene;1-ethenylcyclopenta-1,3-diene;iron(2+) Chemical group [Fe+2].C=1C=C[CH-]C=1.[CH2-]C=C1C=CC=C1 VGBAECKRTWHKHC-UHFFFAOYSA-N 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical group [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000006303 iodophenyl group Chemical group 0.000 description 1
- LXKCAAXANUGTPJ-UHFFFAOYSA-N iodosyl(diphenyl)methanesulfonic acid Chemical compound C1=CC=C(C=C1)C(C2=CC=CC=C2)(S(=O)(=O)O)I=O LXKCAAXANUGTPJ-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C307/02—Monoamides of sulfuric acids or esters thereof, e.g. sulfamic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
- C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Definitions
- the present invention relates to compounds polyionics, process for their preparation and their use as photoinitiators for polymerization or cationic crosslinking of monomers and prepolymers, or for changing the parameters of solubility of certain polymers which can be used as photoresists.
- a polymerization involving a type mechanism cation has many advantages. In particular, it is fast, even at low temperatures, the rate of use of the monomer is high and the sensitivity to contaminants atmospheric, especially oxygen, is weak by comparison to radical or anionic polymerizations.
- Monomers, prepolymers and polymers containing cycloaliphatic epoxide functions and vinyl ethers are used more and more notably in the paints, varnishes, inks, glues and non-stick media.
- ethers vinyl generally appear devoid of toxicity, unlike acrylates or methacrylates.
- the monomers and prepolymers of the epoxy type or of vinyl ether type can be polymerized according to different methods, cationic polymerization being particularly interesting.
- the cationic polymerization catalysts are generally acids within the meaning of Br ⁇ nsted HX (proton donors), or acids within the meaning of Lewis (electron doublet acceptors), the latter operating in the presence of a source co-catalyst of protons. These acids must be strong enough to ensure the stability of the cationic species carried either by the monomer or by the growing macromolecular chain, which means that the corresponding anion X - must have the weakest nucleophilic power. possible.
- the Br ⁇ nsted acids most used as cationic polymerization catalysts are CF 3 SO 3 H, HClO 4 , HBF 4 , HPF 6 , HAsF 6 and HSbF 6 .
- acidic character such as bis (perfluoroalkylsulfonyl) - imide (US-A-4,031,036, Koshar, et al) or bis (perfluoroalkylsulfonyl) methane (US-A-3,632,843, Allen et al.).
- the catalysts can be prepared in situ by heat action.
- ammonium or bis (perfluoroalkylsulfonyl) imide metal US-A-4, 031,036, Koshar, et al.
- bis- (perfluoroalkylsulfonyl) ammonium or amine salts methane US-A-3, 632,843, Allen and al
- bis (perfluoroalkylsulfonyl) imide or bis (perfluoroalkylsulfonyl) methane correspondent then acting as catalyst.
- catalysts do not have however that limited interest due to the need for a prolonged heating at high temperature to obtain the release of the acid, this release being further progressive, and not integral to the initiation.
- the result on the one hand a low reaction speed, and on the other share of poor quality polymers in terms of molecular weight, polydispersity and coloring.
- Acid catalysts can also be prepared in situ by the action of actinic radiation (such as photons whose wavelength corresponds to radiation ultraviolet, visible, ⁇ and X), or ⁇ radiation (electron beam) on an appropriate salt.
- actinic radiation such as photons whose wavelength corresponds to radiation ultraviolet, visible, ⁇ and X
- ⁇ radiation electron beam
- Such salt which has chemical lability under the action of a actinic radiation or ⁇ radiation causing the release of the corresponding acid having a strong catalytic activity, is a photoinitiator.
- Advantages of such a process are multiple: the release of irradiation catalyst is fast and practically total, which leads to a simultaneous initiation of the growth of the chains, and therefore a distribution of the masses more homogeneous with less polydispersity, and better mechanical properties.
- Polymerization can be performed at a relatively low temperature, which prevents decomposition or coloring of materials obtained, as well as the formation of bubbles when a solvent is used or when the reaction mixture contains a volatile additive that we want to keep in the final material and which plays the role of plasticizer.
- these salts When used as photoinitiators of polymerization, they leave, after their decomposition initiated by actinic radiation, fragments which can diffuse on the surface of the material and modify its chemical properties, adhesion or appearance in a notable way.
- these residues In the case of sulfonium, these residues contain thiols and thioethers whose repulsive odor is perceptible to extremely low rates, which limits the use of these salts for specific applications.
- These compounds are most corrosive to metals such as copper or various components of microelectronics. So Kukzynski (USA 5,550,171) considers that the diffusion of the residues is the main cause of failure of computer storage disks.
- Photosensitive polymers formed by the combination of a polydiazonium polycation and a polysulfonate polyanion are described in US-A-5,527,655. Such polymers are used to increase the crosslinking efficiency. The solubility of these complexes is only obtained with diazonium contents clearly lower than 10% by weight in only the presence of a quaternary ammonium salt acting to reduce the electrostatic interactions.
- US-A-5,534,623 describes a composition based on polydiazonium associated with counterions of type PF 6 and intended for the preparation of photoresists. These anions are nonetheless toxic and not compatible with microelectronics since they contain an element capable of contaminating the silicon (B, P, As or Sb).
- the present invention thus relates to a new family of compounds, a process for their preparation, as well as their use as photoinitiators for the polymerization or crosslinking of monomers by route cationic, or for the modification of polymers, in particular when used as photoresists.
- anions X - there may be mentioned the sulfonimide anions [R F SO 2 NSO 2 R ' F ] - in which R F and R' F are chosen independently of one another from the group consisting by perfluoroalkyl groups having from 1 to 10 carbon atoms (preferably CF 3 -, C 2 F 5 -, C 4 F 9 -, C 6 F 13 -, C 8 F 17 - and C 10 F 21 ), and those in which R F and R ' F together form a divalent linear perfluoroalkylene radical having from 1 to 8 carbon atoms.
- R F SO 2 C (Q) SO 2 R ′ F Mention may also be made of the sulfonylmethylide anions [R F SO 2 C (Q) SO 2 R ′ F ] - in which Q is chosen from the group consisting of alkyl, aryl, alkylaryl or arylalkyl groups having at most 30 carbon atoms, perfluoroalkylsulfonyl groups having from 1 to 8 carbon atoms (preferably CF 3 SO 2 -, C 2 F 5 SO 2 -, C 4 F 9 SO 2 -, C 6 F 13 SO 2 - and C 8 F 17 SO 2 -) and perfluoroalkyl radicals having from 1 to 12 carbon atoms (preferably CF 3 -, C 2 F 5 -, C 4 F 9 -, C 6 F 13 -, C 8 F 17 - and C 10 F 21 - ), and R F and R ' F are chosen independently of each other from the group consisting of alkyl groups having from 1 to 10 carbon
- R 1n and R 2n are chosen independently of one another in the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2-ethylhexyl , phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y -or R- [OCH (CH 3 ) CH 2 ] y - in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1 ⁇ y ⁇ 22.
- the polyiodonium compound of the invention responds in one of the formulas (I) or (II), it is presented under the form of a dimer or of a polymer comprising the Iodonium ionic groups in the polymer chain.
- the polyiodonium compound meets one of the formulas (III) or (IV), it takes the form of a polymer in which the iodonium ionic groups are carried by pendant substituents.
- the polysulfonium compounds in which the substituents R 1n , R 3 and R 4 are chosen from the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2ethylhexyl, phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y - or R- [OCH (CH 3 ) CH 2 ] y - in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1 ⁇ y ⁇ 22.
- a compound polysulfonium corresponding to one of the formulas (VII) or (VIII) is in the form of a polymer bearing ionic groupings in the main chain.
- a polysulfonium compound meets one of the formulas (VI) or (IX), it takes the form of a polymer on which the ionic groups are carried by lateral groupings.
- R 1n , R 5 and R 6 are chosen from the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2-ethylhexyl, phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y - or R- [OCH (CH 3 ) CH 2 ] y -in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1 ⁇ y ⁇ 22.
- the part cationic is an organometallic polycation
- the polymers containing the ferrocenium units (in especially those which incorporate the vinylferrocene unit, polyalkylbenzene-iron-cyclopentadiene units), polymers which incorporate nickelocenium units, and polymers that incorporate tricarbonyl units manganesecyclopentadiene.
- the compounds (A + X - ) p of the present invention are generally insoluble in water. They can therefore be prepared by a process consisting in carrying out a metathesis in water or a water / light alcohol mixture (methanol, ethanol, propanol) between compound (A + X 1 - ) p which is a soluble salt of the polycation (A + ) p in which the anion X 1 - has a hydrophilic character, and a water-soluble compound of the anion X - having a highly hydrophilic cation.
- the soluble salts (A + X 1 - ) p of the polycation (A + ) p are preferably chosen from the salts in which the anion X 1 - is chosen from a hydroxide, a chloride, a bromide, a hydrogen sulphate, a dihydrogen phosphate or a methylsulfonate. These anions being strongly solvated by water or light alcohols, they promote solubility.
- the water-soluble compounds or the water / alcohol mixtures of the anion X - are preferably chosen from perhaloalkylsulfonimides and perhaloalkylsulfonyl-methanes, perhaloalkylsulfonimides and perhaloalkylsulfonylmethylides of lithium, sodium, potassium, ammonium, calcium or magnesium.
- perhaloalkylsulfonimides and perhaloalkylsulfonyl-methanes perhaloalkylsulfonimides and perhaloalkylsulfonylmethylides of lithium, sodium, potassium, ammonium, calcium or magnesium.
- the choice of cation depends of course on the ease of obtaining and the minimum hydrophilicity required to cause the solubility.
- the polyionic compound (A + X - ) p of the invention is prepared from a salt (A + X 1 - ) p in which X 1 is a chloride, a bromide, an alkylsulfonate, an alkyloxy-sulfonate or an arylsulfonate, the salts of Na or K of which are insoluble in the usual solvents, it is advantageous to carry out the reaction in the presence of a salt of Na or K of the anions X - .
- solvents mention may be made of acetone, methyl ethyl ketone, acetonitrile, THF, esters such as formates or methyl or ethyl acetate.
- any other ion exchange process can be implemented, for example a method using an ion exchange resin, or a method of selective precipitation.
- the compounds polyionics of the invention are soluble in most usual organic solvents, unlike polyionic compounds of the prior art such as polystyrene-iodonium poly thiaphenylsulfonium despite a high charge density. These are only soluble in water and very polar solvents such as dimethylformamide (DMF) or propylene carbonate depending on the type of counter ion. Water is incompatible, with cationic polymerization reactions and is not not a solvent for most monomers.
- DMF dimethylformamide
- propylene carbonate depending on the type of counter ion.
- Water is incompatible, with cationic polymerization reactions and is not not a solvent for most monomers.
- Solvents such as DMF or propylene carbonate are very difficult to remove due to their temperature high boiling point and they can later contaminate the materials in contact with the products of the polymerization / crosslinking (food industry, serigraphs ).
- the polycations of the invention therefore have could be used as photoinitiators for cationic polymerization. Compared to compounds ionic monomers, they have a certain advantage: when used as photoinitiators, they decompose under the action of actinic radiation without leave residue likely to migrate into the phase polymer obtained.
- the present invention therefore relates to the use of the polyionic compounds (A + X - ) p of the invention as photoinitiators sources of Br ⁇ nsted acids catalysts for polymerization or crosslinking of monomers or prepolymers capable of reacting cationically , or catalysts for modifying the solubility parameters of polymers.
- the process for the polymerization or crosslinking of monomers or prepolymers capable of reacting cationically is characterized in that a compound of the invention is used as photoinitiator source of acid catalyzing the polymerization reaction.
- the choice of groups R 1 to R 8 is made from the above radicals to increase the solubility of said compound in the solvents used for the monomers or prepolymers and according to the properties desired for the final polymer.
- the choice of unsubstituted alkyl radicals gives solubility in slightly polar media.
- the choice of radicals comprising an oxa group or a sulfone will give solubility in polar media.
- the radicals including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group obtained by adding oxygen to the sulfur or phosphorus atoms can confer on the polymer obtained improved properties with regard to adhesion, shine, resistance to oxidation or UV.
- the monomers and prepolymers which can be polymerized or crosslinked using photoinitiators polyionics of the present invention are those which can undergo cationic polymerization.
- the monomers which can be polymerized or crosslinked using a polyionic compound of the invention used as photoinitiator mention may be made of the monomers which have a cyclic ether function, a function cyclic thioether or a cyclic amine function them vinyl compounds, (more particularly ethers vinyl), oxazolines, lactones and lactams.
- ether or thioether type cyclic examples include ethylene oxide, propylene, oxetane, epichlorohydrin, tetrahydrofuran, styrene oxide, cyclohexene oxide, oxide vinylcyclohexene, glycidol, butylene oxide, octylene oxide, glycidyl ethers and esters (e.g. methacrylate or glycidyl acrylate, phenyl glycidyl ether, diglycidyl ether of bisphenol A or its fluorinated derivatives), cyclic acetals having from 4 to 15 carbon atoms (e.g. dioxolane, 1,3-dioxane, 1,3-dioxepane).
- esters e.g. methacrylate or glycidyl acrylate, phenyl glycidyl ether, diglycidyl ether of bisphenol A or its
- vinyl ethers constitute a very important family of monomers sensitive in cationic polymerization.
- vinyl compounds which can be subjected to cationic polymerization in the presence of a polyionic compound of the invention used as photoinitiator, mention may be made, for example, of 1,1dialkylethylenes (e.g. isobutene), monomers vinyl aromatics (for example styrene, ⁇ alkylstyrene, in particular ⁇ -methylstyrene, 4vinylanisole, acenaphthene), N-vinyl compounds (for example N-vinylpyrolidone, N-vinyl formamide or N-vinyl sulfonamides).
- 1,1dialkylethylenes e.g. isobutene
- monomers vinyl aromatics for example styrene, ⁇ alkylstyrene, in particular ⁇ -methylstyrene, 4vinylanisole, acenaphthene
- N-vinyl compounds for example N-vinylpyrolidone, N-
- the prepolymers mention may be made of the compounds in which epoxy groups are carried by a aliphatic chain, an aromatic chain, or a chain heterocyclic, for example the glycidic ethers of bisphenol A ethoxylated with 3 to 15 units of ethylene oxide or propylene, the siloxanes having groups side of the epoxycyclohexene-ethyl type obtained by hydrosilylation of di alkyl, alkylaryl copolymers or diaryl siloxane with methyl hydrogen siloxane in presence of vinylcyclohexene oxide, or of unsaturated ethers difunctionals having a vinyl ether end and a methylvinyl ether (propenyl) end, the products of sol-gel type condensation obtained from triethoxy or trimethoxy silapropylcyclohexene oxide, urethanes incorporating butanediol reaction products monovinyl ether and a higher functionality alcohol or equal to 2 on an aliphatic di or
- the polymerization process according to the invention consists in mixing at least one monomer or prepolymer capable of polymerizing cationically and at least one polyionic compound (A + X - ) p of the invention, and in subjecting the mixture obtained to radiation actinic or ⁇ radiation.
- the reaction mixture is subjected to radiation after having been formed in the form of a thin layer having a thickness less than 5 mm, preferably in the form of a thin film having a thickness less than or equal to 500 ⁇ m.
- the reaction time depends on the thickness of the sample and the power of the source at the active wavelength ⁇ . It is defined by the speed of travel in front of the source, which is between 300 m / min and 1 cm / min. Layers of final material having a thickness greater than 5 mm can be obtained by repeating several times the operation of spreading a layer and treating it with radiation.
- the amount of polyionic photoinitiator (A + X - ) p used is between 0.01 and 15% by weight relative to the weight of monomer or prepolymer, preferably between 0.1 and 5% by weight.
- a polyionic compound (A + X - ) p of the present invention can be used as photoinitiator in the absence of solvent, especially when it is desired to polymerize liquid monomers in which the salt is soluble or easily dispersible. This form of use is particularly interesting, because it eliminates the problems associated with solvents (toxicity, flammability).
- a polyionic compound (A + X - ) p of the present invention can also be used as a photoinitiator in the form of a homogeneous solution in a solvent inert to the polymerization, ready to use and easily dispersible , in particular in the case where the medium to be polymerized or to be crosslinked has a high viscosity.
- volatile solvents such as acetone, methyl ethyl ketone and acetonitrile. These solvents will simply serve to dilute the products to be polymerized or crosslinked (to make them less viscous, especially when it is a prepolymer). They will be removed after polymerization or crosslinking by drying. Mention may also be made of non-volatile solvents.
- a non-volatile solvent is used in the same way as a volatile solvent, to dilute the products which it is desired to polymerize or crosslink, and to dissolve the polyionic compound) (A + X - ) p of the invention used as photoinitiator, but in addition it will remain in the material formed and it will thus act as a plasticizer.
- a plasticizer for example, mention may be made of propylene carbonate, ⁇ butyrolactone, ether-esters of mono-, di-, triethylene or propylene glycols, ether-alcohols of mono-, di-, tri-ethylene or propylene glycols , plasticizers such as esters of phthalic acid or citric acid.
- a reactive compound vis-à-vis is used as solvent or diluent of polymerization, which is a compound of low molecular mass and low viscosity which will play the both the role of polymerizable monomer and the role of solvent or diluent for more viscous monomers or prepolymers used together.
- these monomers having served as solvent are part of the network macromolecular finally obtained, their integration being greater in the case of bi-functional monomers.
- the material obtained after irradiation no longer contains products with low molecular weight and tension appreciable vapor, or likely to contaminate objects with which the polymer is in contact.
- a reactive solvent can be chosen from mono and di vinyl ethers of mono-, di-, tri-, tetraethylene and propylene glycols, N-methylpyrolidone, 2propenylether propylene carbonate marketed by example under the name PEPC by the company ISP, New Jersey, United States.
- the radiation can be chosen from ultraviolet radiation, visible radiation, X-rays, ⁇ rays and ⁇ radiation.
- ultraviolet light it may be advantageous to add to the photoinitiators of the invention photosensitizers intended to allow efficient photolysis with wavelengths less energetic than those corresponding to the maximum absorption of the photoinitiator, such as those emitted by industrial devices, ( ⁇ ⁇ 300 nm for mercury vapor lamps in particular).
- Such additives are known, and by way of nonlimiting examples, mention may be made of anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine, tetracene, xanthone, thioxanthone, acetophenone, benzophenone, 1,3,5-triaryl-2pyrazolines and their derivatives, in particular the derivatives of substitution on the aromatic nuclei by alkyl, oxa- or aza-alkyl radicals allowing among others to change the wavelength of absorption.
- Isopropylthioxantone is an example of a preferred photosensitizer when a polyiodonium compound A p + pX - according to the invention is used as a photoinitiator.
- ultraviolet radiation is particularly preferred. Of a hand it is more convenient to use than the others radiation mentioned.
- photoinitiators are generally directly sensitive to UV rays and photosensitizers are all the more effective as the energy difference ( ⁇ ) is lower.
- the polyionic compounds (A + X - ) p of the invention can also be used in combination with initiators of the radical type generated thermally or by the action of actinic radiation. It is thus possible to polymerize or crosslink mixtures of monomers or prepolymers containing functions whose polymerization modes are different, for example monomers or prepolymers polymerizing by the radical route and monomers or prepolymers polymerizing by the cationic route. This possibility is particularly advantageous for creating interpenetrating networks having physical properties different from those which would be obtained by simple mixing of the polymers derived from the corresponding monomers.
- the vinyl ethers are not or are not very active by radical initiation.
- a radical initiator such as the esters or the amides of fumaric acid, of maleic acid, of acrylic or methacrylic acid, of itaconic acid, of acrylonitrile, methacrylonitrile, maleimide and its derivatives, form, in the presence of vinyl ethers rich in electrons, charge transfer complexes giving alternating polymers 1: 1 by radical initiation.
- An initial excess of vinyl monomers with respect to this stoichiometry makes it possible to preserve polymerizable functions by pure cationic initiation.
- the following commercial products may be mentioned as initiators: Irgacure 184®, Irgacure 651®, Irgacure 261® Quantacure DMB®, Quantacure ITX®.
- a mixture of a radical initiator heat dissociable and a cationic photoinitiator according to the invention makes it possible to carry out polymerizations or sequential cross-links, first under the action of heat, then under the action of actinic radiation.
- Radical initiators can be for example Irgacure® 651 allowing priming of radical polymerizations at wavelengths 365 nm.
- a subject of the invention is also the use of the polyionic compounds (A + X - ) p of the invention for the chemical amplification reactions of photoresists for microlithography.
- a film of a material comprising a polymer and a polyionic compound (A + X - ) p of the invention is subjected to irradiation.
- the irradiation causes the formation of HX acid, which catalyzes the decomposition or transformation of the polymer.
- the monomers formed or the transformed polymer are eliminated and an image of the unexposed parts remains.
- polymer compounds comprising vinyl units carrying an ionic substituent.
- these compounds there may be mentioned the polyiodonium salts corresponding to formula (III), the polysulfonium salts corresponding to formula (VI), the polyacylsulfonium corresponding to formula (XI), the polydiazonium corresponding to formula (XV) , the salts of organometallic complexes corresponding to formula (XVIII).
- These compounds make it possible to obtain, after photolysis, products which are not volatile and therefore not odorous when it is a question of sulphides.
- the polysulfonium which are particularly effective as a photoinitiator, the phenacylsulfonium and the polymers and copolymers of vinyl ferrocenium which can be obtained easily.
- polymers containing ester units or aryl ether units of tertiary alcohol for example poly (phthalaldehydes), bisphenol polymers A and a diacid, polytertiobutoxycarbonyl oxystyrene, polytertiobutoxy-a-methyl styrene, polyditertiobutylfumarate-co-allyltrimethylsilane and polyacrylates of a tertiary alcohol, in particular tertiary butyl polyacrylate.
- polymers containing ester units or aryl ether units of tertiary alcohol for example poly (phthalaldehydes), bisphenol polymers A and a diacid, polytertiobutoxycarbonyl oxystyrene, polytertiobutoxy-a-methyl styrene, polyditertiobutylfumarate-co-allyltrimethylsilane and polyacrylates of a tertiary alcohol, in particular ter
- the polyionic compounds (A + X - ) p of the present invention which exhibit high thermal stability, offer numerous advantages over the salts known from the prior art. They have priming and propagation speeds comparable to or higher than those obtained using coordination anions of the PF 6 - , AsF 6 - and especially SbF 6 - type .
- the salts M + X - in which M is an alkali metal and X an anion identical to the anion of a compound of the present invention are known to be easily solvated in polymers, of which they slightly increase the glass transition temperature.
- the diffusion coefficient of the anion X - is higher than that of hexafluorometallate anions or tetrafluoroborate anions or phenylborate anions.
- Another advantageous advantage of the polyionic compounds (A + X - ) p of the invention is the absence of toxic elements such as P, As or Sb, these elements being moreover considered as contaminating agents in the processes of micro -electronic.
- a compound comprising iodophenyl groups was prepared by transforming the aromatic nuclei of a polystyrene sample (M w 6000) by iodization of the polystyrene, oxidation to iodosoacetate by the acetic acid / acetic anhydride / hydrogen peroxide mixture according to the method described. by Yamada et al. (Die Makromolecular Chemie, (1972), 152 , 153-162). 10 g of the compound thus prepared were suspended in a mixture of 30 ml of methanesulfonic acid and 5 ml of butoxybenzene maintained at 0 ° C for 4 hours.
- the reaction product was poured into 400 ml of a 2: 1 v / v ether: isopropanol mixture and the precipitate was separated by filtration, washed with THF and dried. 8 g of the polyiodonium methanesulfonate thus obtained were suspended in 50 ml of water and 10 g of lithium salt of bis (nonafluorobutanesulfonyl) imide lithium dissolved in 25 ml of water were added. The mixture was stirred for 1 hour and separated by filtration.
- the yield of ion exchange (metathesis) is quantitative for obtaining bis (nonafluorobutanesulfonyl) poly (vinylphenyl- (4-butoxyphenyl) -4-iodonium imide) imide.
- the structure of the polymer is:
- the polysulfonium salt was obtained:
- the viscous solution obtained was centrifuged to remove toluenesulfonate sodium, then precipitated by water. We thus obtained a yellow powder soluble in the usual solvents.
- the phenoxyethylvinyl ether was prepared by reacting the chloroethylvinyl ether with the sodium phenate, then polymerization in dichloromethane initiated by TiCl 4 was carried out at -10 ° C. By reacting 8.2 g of the polymer thus obtained with 9.8 g of phenyliodosotoluene sulfonate in 40 ml of an equivolumic mixture of acetic acid and dichloromethane, a polyiodonium was obtained which was precipitated with ether.
- the ion exchange reaction was then carried out in the same manner as in Example 3 between 12 g of polymer and 7 g of sodium salt of the bis (trifluoromethanesulfonyl) imide. After precipitation and washing with water, a sticky mass was obtained which can be used in 50% solution in methyl ethyl ketone.
- oligomer containing iodonium groups was prepared according to the method described in J. Polym. Sci., Polym. Lett. (1976), 14 , 65 in the form of bromide, by the action of 5.7 g of 1,4-bis (diacetoxyiodo) phenylene on 20 ml of 1,3-diphenylpropane in 300 ml of acetic anhydride and 40 ml of sulfuric acid at 0 ° C. The mixture was poured into 1 l of water containing 80 g of sodium bromide and 100 g of sodium acetate. The precipitate was filtered, washed with ether and dried.
- a bromide of an identical polyiodonium cation has only negligible solubility in the most polar solvents known, such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), or hexamethylphosphoramide (HMPA).
- DMSO dimethylsulfoxide
- DMF dimethylformamide
- HMPA hexamethylphosphoramide
- solubility properties of certain polyionic compounds of the present invention were compared with the properties of a poly (iodonium) prepared according to Crivello & Lam (J. Polym. Sci .; Polymer Chemistry, (1979), 17 , 3845-3858) .
- the polyiodonium according to Crivello et al was obtained by a trans-addition of (4,4'-N-maleimido) diphenyliodonium chloride with 1,10-decanethiol in m-cresol in the presence of a tertiary base, followed by '' a metathesis in the presence of NaPF 6 .
- the compounds of the present invention were prepared in the same way, but replacing for metathesis NaPF 6 with one of the following salts: Na + (CF 3 SO 2 ) 2 N - , Na + (CF 3 SO 2 ) N (SO 2 C 4 F 9 ) - , Na + (CF 3 SO 2 ) 3 C - .
- a polythioether was prepared by reacting 15 g of dimercaptohexane with 18.67 g of 1.2 bis (2-chloroethoxy) ethane in 200 ml of N-methylpyrrolidone at 150 ° C in the presence of 10 g of potassium carbonate.
- the polymer obtained was precipitated in water and purified by several dissolution (CH 2 Cl 2 ) / precipitation (diethyl ether) operations, then separated by centrifugation in a single container. The polymer is in the form of a sticky mass.
- a polythioether similar to that of the previous example was prepared by reacting 8 g of 2-mercaptoethyl ether with 15.3 g of a, a-dibromo-m-xylene in 100 ml of dimethylformamide at 80 ° C in the presence of 4 g of potassium carbonate.
- the polymer was precipitated in water and purified as before.
- 10 g of the polymer were dissolved in 120 ml of hexane and 11.5 was added dropwise g of bromoacetyl-4-octyloxybenzene). The mixture was heated to reflux at 60 ° C.
- DVE-3 triethylene glycol divinyl ether
- the polymer was precipitated in ether and purified by several dissolution (CH 2 Cl 2 ) / precipitation (diethyl ether) operations.
- the polymer was obtained in the form of a white solid, with a yield of 63%.
- 8.2 g of the polymer were dissolved in 120 ml of dichloroethane (C 2 H 4 Cl 2 ) and the solution of CpFe (CO) 2 Br in acetonitrile previously prepared was added. The mixture was heated to reflux. A precipitate formed with concomitant evolution of carbon monoxide. The reaction was continued 2 hours after the appearance of the precipitate.
- the poly (areneferrocenium) bromide was separated by filtration and washed with dichloromethane and acetonitrile. 3 g of the polyionic compound were dissolved in 50 ml of water to which were added 3.8 g of lithium salt of (nonafluorobutanesulfonyl) - (trifluoromethylsulfonyl) imide (Li [C 4 F 9 SO 2 NSO 2 CF 3 ]) in 25 ml of water; a precipitate formed immediately and the stirring was continued for 1 h. The polymer was separated by filtration and dried. It was obtained with a quantitative yield.
- the polymer was precipitated in methanol and purified by three dissolution (THF) / precipitation (methanol) operations. To 5.4 g of this polymer in solution in dichloromethane, 2.4 g of [bis (trifluoroacetoxy) iodo] benzene were added. The reaction product was poured into 100 ml of ether and the precipitate was separated by centrifugation.
- a metathesis allowing the trifluoroacetate anion to be replaced by the tris (trifluoromethanesulfonyl) methylide anion was carried out in water (100 ml) between 4.2 g of the poly (cation) and 3.1 g of the sodium salt tris ( trifluoromethanesulfonyl) sodium methylide dissolved in 25 ml of water.
- the polymer has been separated by centrifugation and is in the form of a blue gummy mass soluble in most solvents, including at contents> 3% in silicone oils.
- the structure of the polymer is as follows:
- a diazonium oligomer was prepared according to the method described in U.S. 2,714,066 by condensation of 4-diazodiphenylamine chlorozincate with formaldehyde. 25 g of this polyionic compound were dissolved in 500 ml water kept at 0 ° C and containing 50 g of sodium acetate and 28 g of sodium di-salt of ethylene diamine acid tetraacetic (EDTA). 24 g of salt were then added. bis (trifluoromethanesulfonyl) imide sodium solution in 50 ml of water. The polyionic compound has been separated by filtration and dried (quantitative yield), and stored at 0 ° C protected from light. This compound is very slightly soluble in usual organic solvents polar such as MEK, and soluble in the monomers of type DVE-3 or PEPC, or glycidic ethers.
- the polyionic compounds of the previous examples were used in an amount of 1% by weight in different monomers and irradiated by UV radiation at 254 nm with a power of 1900 mW / cm 2 for a period of 5 seconds, followed by a period of 10 minutes allowing the propagation of the species generated in the environment (aftercare).
- the results are shown in the table below.
Abstract
L'invention concerne de nouveaux polymères polyioniques dans lesquels la partie cationique, constituée par des unités récurrentes biaryliodonium, arylsulfonium, arylacylsulfonium, diazonium ou organométalliques, est associée à des anions sulfonylimidures ou sulfonylméthylures. Ces polymères sont utiles comme photoamorceurs pour la polymérisation ou la réticulation cationique ou pour la modification des paramètres de solubilité de polymères utilisés notamment comme photorésists.The invention relates to new polyionic polymers in which the cationic part, consisting of repeating units biaryliodonium, arylsulfonium, arylacylsulfonium, diazonium or organometallic, is associated with sulfonylimide or sulfonylmethylide anions. These polymers are useful as photoinitiators for the polymerization or cationic crosslinking or for the modification of the solubility parameters of polymers used in particular as photoresists.
Description
La présente invention concerne des composés polyioniques, leur procédé de préparation et leur utilisation comme photoamorceurs pour la polymérisation ou la réticulation par voie cationique de monomères et de prépolymères, ou pour la modification des paramètres de solubilité de certains polymères qui peuvent être utilisés comme photorésists.The present invention relates to compounds polyionics, process for their preparation and their use as photoinitiators for polymerization or cationic crosslinking of monomers and prepolymers, or for changing the parameters of solubility of certain polymers which can be used as photoresists.
Une polymérisation mettant en jeu un mécanisme de type cationique présente de nombreux avantages. En particulier, elle est rapide, même à basse température, le taux d'utilisation du monomère est élevé et la sensibilité aux contaminants atmosphériques, notamment l'oxygène, est faible par comparaison aux polymérisations radicalaires ou anioniques.A polymerization involving a type mechanism cation has many advantages. In particular, it is fast, even at low temperatures, the rate of use of the monomer is high and the sensitivity to contaminants atmospheric, especially oxygen, is weak by comparison to radical or anionic polymerizations.
Les monomères, les prépolymères et les polymères contenant des fonctions époxydes cycloaliphatiques et les éthers vinyliques sont utilisés de plus en plus notamment dans l'industrie des peintures, des vernis, des encres, des colles et des supports anti-adhésifs. De plus, les éthers vinyliques apparaissent d'une manière générale dénués de toxicité, contrairement aux acrylates ou aux méthacrylates. Les monomères et les prépolymères du type époxydes ou du type éther vinylique peuvent être polymérisés selon différentes méthodes, la polymérisation cationique étant particulièrement intéressante.Monomers, prepolymers and polymers containing cycloaliphatic epoxide functions and vinyl ethers are used more and more notably in the paints, varnishes, inks, glues and non-stick media. In addition, ethers vinyl generally appear devoid of toxicity, unlike acrylates or methacrylates. The monomers and prepolymers of the epoxy type or of vinyl ether type can be polymerized according to different methods, cationic polymerization being particularly interesting.
Les catalyseurs de polymérisation cationique sont
d'une manière générale des acides au sens de Brønsted HX
(donneurs de protons), ou des acides au sens de Lewis
(accepteurs de doublets électroniques), ces derniers fonctionnant
en présence d'un co-catalyseur source de protons.
Il est nécessaire que ces acides soient suffisamment forts
pour assurer la stabilité de l'espèce cationique portée
soit par le monomère, soit par la chaíne macromoléculaire
en croissance, ce qui signifie que l'anion correspondant X-
doit posséder le pouvoir nucléophile le plus faible
possible. Les acides de Brønsted les plus utilisés comme
catalyseurs de polymérisation cationique sont CF3SO3H,
HClO4, HBF4, HPF6, HAsF6 et HSbF6. Ces acides se classent
comme suit, en ce qui concerne les vitesses d'amorçage, de
propagation ainsi que l'obtention des masses moléculaires
les plus élevées :
Plus récemment, on a également utilisé des composés à caractère acide tels que le bis(perfluoroalkylsulfonyl)- imide (US-A-4,031,036, Koshar, et al) ou le bis(perfluoroalkylsulfonyl)méthane (US-A-3,632,843, Allen et al.).More recently, compounds have also been used. acidic character such as bis (perfluoroalkylsulfonyl) - imide (US-A-4,031,036, Koshar, et al) or bis (perfluoroalkylsulfonyl) methane (US-A-3,632,843, Allen et al.).
Il est connu que la préparation in-situ de catalyseurs de polymérisation présente de nombreux avantages. La production in situ de l'acide capable de catalyser la réticulation d'un monomère permet en effet de mettre en forme un monomère ou un prépolymère fluide (matériau thermoplastique ou solution) et de lui donner ses propriétés définitives par exemple par simple action d'un rayonnement. Cette technique est très utilisée pour les encres, les peintures, les films adhésifs et les films anti-adhésifs. Il faut noter en outre que la préparation de l'acide in situ à partir d'un sel permet dans de nombreux cas d'éviter le stockage et la manipulation de composés acides plus corrosifs que les sels correspondants.It is known that the in situ preparation of catalysts polymerization has many advantages. The production in situ acid capable of catalyzing the crosslinking of a monomer in fact makes it possible to forms a fluid monomer or prepolymer (thermoplastic material or solution) and give it its properties definitive for example by simple action of radiation. This technique is widely used for inks, paints, adhesive films and non-stick films. It should also be noted that the preparation of the acid in situ from a salt in many cases avoids storage and handling of more acidic compounds corrosive than the corresponding salts.
Les catalyseurs peuvent être préparés in situ par action de chaleur. Par exemple, des sels d'ammonium ou de métal de bis (perfluoroalkylsulfonyl) imide (US-A-4, 031,036, Koshar, et al.) ou des sels d'ammonium ou d'amine de bis-(perfluoroalkylsulfonyl) méthane (US-A-3, 632,843, Allen et al) ont été utilisés pour obtenir in-situ, par chauffage, le bis (perfluoroalkylsulfonyl) imide ou le bis (perfluoroalkylsulfonyl)méthane correspondant, agissant ensuite comme catalyseur. Ces catalyseurs, dits "latents", ne présentent cependant qu'un intérêt limité du fait de la nécessité d'un chauffage prolongé à température élevée pour obtenir la libération de l'acide, cette libération étant en outre progressive, et non pas intégrale à l'initiation. Il en résulte d'une part une faible vitesse de réaction, et d'autre part des polymères de qualité médiocre en ce qui concerne la masse moléculaire, la polydispersité et la coloration.The catalysts can be prepared in situ by heat action. For example, ammonium or bis (perfluoroalkylsulfonyl) imide metal (US-A-4, 031,036, Koshar, et al.) Or bis- (perfluoroalkylsulfonyl) ammonium or amine salts methane (US-A-3, 632,843, Allen and al) were used to obtain in situ, by heating, bis (perfluoroalkylsulfonyl) imide or bis (perfluoroalkylsulfonyl) methane correspondent, then acting as catalyst. These catalysts, called "latent", do not have however that limited interest due to the need for a prolonged heating at high temperature to obtain the release of the acid, this release being further progressive, and not integral to the initiation. The result on the one hand a low reaction speed, and on the other share of poor quality polymers in terms of molecular weight, polydispersity and coloring.
Les catalyseurs acides peuvent également être préparés in situ par action d'un rayonnement actinique (tel que les photons dont la longueur d'onde correspond au rayonnement ultraviolet, visible, γ et X) , ou d'un rayonnement β (faisceau d'électrons) sur un sel approprié. Un tel sel, qui présente une labilité chimique sous l'action d'un rayonnement actinique ou d'un rayonnement β amenant la libération de l'acide correspondant ayant une forte activité catalytique, est un photoamorceur. Les avantages d'un tel procédé sont multiples : la libération du catalyseur par irradiation est rapide et pratiquement totale, ce qui entraíne une initiation simultanée de la croissance des chaínes, et donc un répartition des masses plus homogène avec une moindre polydispersité, et de meilleures propriétés mécaniques. La polymérisation peut être effectuée à une température relativement basse, ce qui évite une décomposition ou une coloration des matériaux obtenus, ainsi que la formation de bulles lorsqu'un solvant est utilisé ou lorsque le mélange réactionnel contient un additif volatil que l'on souhaite conserver dans le matériau final et qui joue le rôle de plastifiant.Acid catalysts can also be prepared in situ by the action of actinic radiation (such as photons whose wavelength corresponds to radiation ultraviolet, visible, γ and X), or β radiation (electron beam) on an appropriate salt. Such salt, which has chemical lability under the action of a actinic radiation or β radiation causing the release of the corresponding acid having a strong catalytic activity, is a photoinitiator. Advantages of such a process are multiple: the release of irradiation catalyst is fast and practically total, which leads to a simultaneous initiation of the growth of the chains, and therefore a distribution of the masses more homogeneous with less polydispersity, and better mechanical properties. Polymerization can be performed at a relatively low temperature, which prevents decomposition or coloring of materials obtained, as well as the formation of bubbles when a solvent is used or when the reaction mixture contains a volatile additive that we want to keep in the final material and which plays the role of plasticizer.
On connaít la capacité de différents sels (hexafluoroantimonates, hexafluoroarséniates, hexafluoroplatinates et tétrafluoroborates) d'aryldiazonium, d'aryliodonium, d'arylsulfonium, d'arylacylsulfonium ou d'arèneferrocénium à former, sous l'action de radiations actiniques, des acides (respectivement HSbF6, HAsF6, HPF6, HBF4) utilisables comme catalyseurs de polymérisation cationique. Néanmoins, tous ces sels présentent une toxicité non négligeable, associée principalement à l'élément central de la partie anionique, Sb, As, P et B ainsi qu'aux ions fluor pouvant être libérés au cours de la réaction de photolyse ou lors du traitement ultérieur du polymère (fusion, extrusion...). Pour fixer un ordre de grandeur, l'hexafluoroantimonate de diphényliodonium possède un LD50 de 40 mg/kg (mesuré selon le test n°10929 TAR) et entre dans la catégorie des produits classifiés "hautement toxiques".We know the ability of different salts (hexafluoroantimonates, hexafluoroarseniates, hexafluoroplatinates and tetrafluoroborates) of arldiazonium, aryliodonium, arylsulfonium, arylacylsulfonium or areneferrocenium to form acids (respectively HSbF 6 , HAsF 6 , HPF 6 , HBF 4 ) usable as cationic polymerization catalysts. Nevertheless, all of these salts have a non-negligible toxicity, associated mainly with the central element of the anionic part, Sb, As, P and B as well as with the fluorine ions which can be released during the photolysis reaction or during the treatment. the polymer (fusion, extrusion ...). To fix an order of magnitude, diphenyliodonium hexafluoroantimonate has an LD50 of 40 mg / kg (measured according to test No. 10929 TAR) and falls into the category of products classified as "highly toxic".
D'autres sels contenant des cations de la même nature, mais des anions moins toxiques ont alors été proposés. Ainsi, US-A-5,554,664 décrit des sels dont l'anion est choisi parmi les tris(alkylsulfonyl)méthylures, les tris(arylsulfonyl)méthylures, les bis (alkylsulfonyl) imidures et les bis(arylsulfonyl)imidures dans lesquels le groupe alkyle ou le groupe aryle est perfluoré ou fortement fluoré, et dont le cation est un iodonium, un sulfonium ou un organométallique. Ces composés peuvent être utilisés notamment comme initiateurs de polymérisation après activation in situ. Lorsque ces sels sont utilisés comme photoamorceurs de polymérisation, ils laissent, après leur décomposition initiée par le rayonnement actinique, des fragments qui peuvent diffuser à la surface du matériau et en modifier les propriétés chimiques, l'adhésion ou l'apparence d'un manière notable. Dans les cas des sels de sulfonium, ces résidus contiennent des thiols et des thioéthers dont l'odeur repoussante est perceptible à des taux extrêment faibles, ce qui limite l'utilisation de ces sels à des applications particulières. Ces composés sont des plus corrosifs vis à vis des métaux comme le cuivre ou divers composants de la microélectronique. Ainsi Kukzynski (USA 5,550,171) considère que la diffusion des résidus catalytiques est la cause principale de défaillance des disques de stockage informatique.Other salts containing cations of the same nature, but less toxic anions were then proposed. Thus, US-A-5,554,664 describes salts whose anion is chosen from tris (alkylsulfonyl) methylides, tris (arylsulfonyl) methylides, bis (alkylsulfonyl) imides and the bis (arylsulfonyl) imides in which the group alkyl or the aryl group is perfluorinated or strongly fluorinated, and whose cation is an iodonium, a sulfonium or an organometallic. These compounds can be used especially as polymerization initiators after in situ activation. When these salts are used as photoinitiators of polymerization, they leave, after their decomposition initiated by actinic radiation, fragments which can diffuse on the surface of the material and modify its chemical properties, adhesion or appearance in a notable way. In the case of sulfonium, these residues contain thiols and thioethers whose repulsive odor is perceptible to extremely low rates, which limits the use of these salts for specific applications. These compounds are most corrosive to metals such as copper or various components of microelectronics. So Kukzynski (USA 5,550,171) considers that the diffusion of the residues is the main cause of failure of computer storage disks.
Des polymères photosensibles constitués par l'association d'un polycation polydiazonium et d'un polyanion polysulfonate sont décrits dans US-A-5,527,655. De tels polymères sont utilisés pour augmenter l'efficacité de réticulation. La solubilité de ces complexes n'est obtenue qu'avec des teneurs en diazonium nettement inférieures à 10% en poids en uniquement en présence d'un sel d'ammonium quaternaire agissant pour diminuer les interactions electrostatiques. US-A-5,534,623 décrit une composition à base de polydiazonium associé à des contre-ions du type PF6 et destiné à la préparation de photorésists. Ces anions sont néanmoins toxiques et non compatibles avec la microélectronique car contenant un élement suceptible de contaminer le silicium (B, P, As ou Sb). Photosensitive polymers formed by the combination of a polydiazonium polycation and a polysulfonate polyanion are described in US-A-5,527,655. Such polymers are used to increase the crosslinking efficiency. The solubility of these complexes is only obtained with diazonium contents clearly lower than 10% by weight in only the presence of a quaternary ammonium salt acting to reduce the electrostatic interactions. US-A-5,534,623 describes a composition based on polydiazonium associated with counterions of type PF 6 and intended for the preparation of photoresists. These anions are nonetheless toxic and not compatible with microelectronics since they contain an element capable of contaminating the silicon (B, P, As or Sb).
Il est également connu d'utiliser des acides générés à l'aide d'un rayonnement actinique pour dégrader les résines contenues dans un film constituant un photorésist. Cette technique est particulièrement efficace pour les photorésists à amplification chimique, dans lesquels de très faibles quantités de protons catalysent la décomposition de groupements tels que des esters contenant un groupement dérivé d'un alcool tertiaire (tel que par exemple un groupement tertiobutyle), faisant partie d'une chaíne macromoléculaire. Elle permet ainsi de modifier les paramètres de solubilité de la résine exposée à un rayonnement actinique et d'effectuer des opérations de masquage et de gravure sélectives telles qu'utilisées en microélectronique.It is also known to use acids generated from using actinic radiation to degrade resins contained in a film constituting a photoresist. This technique is particularly effective for photoresists with chemical amplification, in which very small amounts of protons catalyze the decomposition of groups such as esters containing a group derived from a tertiary alcohol (such as for example a tertiobutyle group), part of a chain macromolecular. It allows you to modify the solubility parameters of the resin exposed to a actinic radiation and to perform operations of selective masking and etching as used in microelectronics.
Lorsqu'une composition de photoresists ou une composition de résine à d'amplification chimique utilisée en microlithographie contient un photoamorceur, on considère que la diffusion des espèces ioniques de l'initiateur ou de l'acide formé détermine la limite de résolution spaciale, qui est de plusieurs dizaines de microns avec les initiateurs non polymères. Or il est demandé actuellement des résolutions inférieures à 1 micron pour l'industrie électroniques des microprocesseurs et des mémoires.When a photoresist composition or a chemically amplified resin composition used in microlithography contains a photoinitiator, we considers that the diffusion of the ionic species of the initiator or acid formed determines the limit of spatial resolution, which is several tens of microns with non-polymeric initiators. But, he is currently requests resolutions below 1 micron for the electronics industry of microprocessors and memories.
Les inventeurs ont maintenant trouvé de nouveaux composés ioniques qui permettent d'obtenir sous l'action d'un rayonnement actinique ou d'un rayonnement β, des acides qui se révèlent bons catalyseurs de polymérisation cationique ou de modification de polymères. Ces matériaux, contrairement à ce qui est attendu du comportement inhérent aux polyélectrolytes, c'est à dire une solubilité limitée à des solvants de très forte polarité, sont solubles ou dispersables dans les solvants organiques habituels ou les monomères destinés a être polymérisés ou leurs mélanges.The inventors have now found new ionic compounds which allow to get under the action actinic radiation or β radiation, acids which prove to be good polymerization catalysts cationic or polymer modification. These materials, contrary to what is expected from inherent behavior polyelectrolytes, i.e. a solubility limited to solvents of very high polarity, are soluble or dispersible in the usual organic solvents or monomers intended to be polymerized or mixtures thereof.
La présente invention a ainsi pour objet une nouvelle famille de composés, un procédé pour leur préparation, ainsi que leur utilisation comme photoamorceurs pour la polymérisation ou la réticulation de monomères par voie cationique, ou pour la modification de polymères, notamment lorsqu'ils sont utilisés comme photorésists.The present invention thus relates to a new family of compounds, a process for their preparation, as well as their use as photoinitiators for the polymerization or crosslinking of monomers by route cationic, or for the modification of polymers, in particular when used as photoresists.
Un composé de la présente invention est un composé ionique oligomère ou polymère constitué par une partie polycationique (A+)p comprenant plusieurs unités ionium et par un nombre d'anions X- suffisant pour assurer la neutralité électrique du composé, et il est caractérisé en ce que :
- les unités onium sont choisies dans le groupe constitué par les biaryliodonium, les arylsulfonium, les arylacylsulfonium, les diazonium, les cations organométalliques comprenant un métal de transition complexé par au moins un cycle insaturé comprenant de 4 à 12 atomes de carbone ;
- X- est un anion imidure [RFSO2NSO2R'F]- ou un anion
méthylure [RFSO2C(Q)SO2R'F]- dans lesquels
- 1) Q représente :
- H-, Cl-, F-, Br- ou CN- ;
- un radical alkyle ayant de 1 à 30 atomes de carbone ;
- un radical aryle ou alkylaryle ou arylalkyle ayant de 6 à 30 atomes de carbone ;
- un groupe R"F ou un groupe R"FSO2 ;
- 2) RF et R'F, ainsi que R"F le cas échéant lorsque X- est un anion méthylure, sont choisis indépendamment l'un de l'autre dans le groupe constitué par le fluor, les groupements perhaloalkyles ayant de 1 à 30 atomes de carbone, les groupements (perhaloalkyl)alkyloxy, les groupements cycloaliphatiques perhalogénés ayant de 3 à 30 atomes de carbone contenant éventuellement des hétéroatomes choisis parmi O et N, et/ou portant éventuellement au moins un chaínon perhaloalkyle, les groupements aryles perhalogénés ayant de 6 à 30 atomes de carbone ; ou bien
- 3) RF et R'F forment ensemble un radical divalent formant un cycle respectivement avec le groupe -SO2-N-SO2- ou avec le groupe -SO2-C(Q)-SO2-, ou bien, lorsque X- est un anion méthylure, R"F forme avec l'un des radicaux RF ou R'F un radical divalent formant un cycle respectivement avec le groupe -SO2-C-SO2- ou avec le groupe -SO2-C-, ledit radical divalent étant choisi parmi les radicaux alkylènes perfluorés ayant de 2 à 12 atomes de carbone, le troisième radical présent le cas échéant étant choisi parmi les radicaux monovalents cités ci-dessus en 2) ;
- 4) p représente le nombre d'unités onium, et par conséquent le nombre d'anions X- associés.
- the onium units are chosen from the group consisting of biaryliodonium, arylsulfonium, arylacylsulfonium, diazonium, organometallic cations comprising a transition metal complexed by at least one unsaturated ring comprising from 4 to 12 carbon atoms;
- X - is an imide anion [R F SO 2 NSO 2 R ' F ] - or a methylide anion [R F SO 2 C (Q) SO 2 R' F ] - in which
- 1) Q represents:
- H-, Cl-, F-, Br- or CN-;
- an alkyl radical having from 1 to 30 carbon atoms;
- an aryl or alkylaryl or arylalkyl radical having from 6 to 30 carbon atoms;
- an R " F group or an R" F SO 2 group ;
- 2) R F and R ' F , as well as R " F where appropriate when X - is a methylide anion, are chosen independently of one another from the group consisting of fluorine, the perhaloalkyl groups having from 1 to 30 carbon atoms, (perhaloalkyl) alkyloxy groups, perhalogenated cycloaliphatic groups having from 3 to 30 carbon atoms optionally containing heteroatoms chosen from O and N, and / or optionally carrying at least one perhaloalkyl chain, perhalogenated aryl groups having from 6 to 30 carbon atoms; or
- 3) R F and R ' F together form a divalent radical forming a cycle respectively with the group -SO 2 -N-SO 2 - or with the group -SO 2 -C (Q) -SO 2 -, or alternatively, when X - is a methylide anion, R " F forms with one of the radicals R F or R ' F a divalent radical forming a ring respectively with the group -SO 2 -C-SO 2 - or with the group -SO 2 - C-, said divalent radical being chosen from perfluorinated alkylene radicals having from 2 to 12 carbon atoms, the third radical present, where appropriate, being chosen from monovalent radicals mentioned above in 2);
- 4) p represents the number of onium units, and therefore the number of associated X - anions.
Comme exemples particulièrement intéressants d'anions X-, on peut citer les anions sulfonimidures [RFSO2NSO2R'F]- dans lesquels RF et R'F sont choisis indépendamment l'un de l'autre dans le groupe constitué par les groupements perfluoroalkyles ayant de 1 à 10 atomes de carbone (de préférence CF3-, C2F5-, C4F9-, C6F13-, C8F17- et C10F21), et ceux dans lesquels RF et R'F forment ensemble un radical perfluoroalkylène linéaire divalent ayant de 1 à 8 atomes de carbone.As particularly interesting examples of anions X - , there may be mentioned the sulfonimide anions [R F SO 2 NSO 2 R ' F ] - in which R F and R' F are chosen independently of one another from the group consisting by perfluoroalkyl groups having from 1 to 10 carbon atoms (preferably CF 3 -, C 2 F 5 -, C 4 F 9 -, C 6 F 13 -, C 8 F 17 - and C 10 F 21 ), and those in which R F and R ' F together form a divalent linear perfluoroalkylene radical having from 1 to 8 carbon atoms.
On peut également citer les anions sulfonylméthylures [RFSO2C(Q)SO2R'F]- dans lesquels Q est choisi dans le groupe constitué par les groupements alkyles, aryles, alkylaryles ou arylalkyles ayant au plus 30 atomes de carbone, les groupements perfluoroalkylsulfonyles ayant de 1 à 8 atomes de carbone (de préférence CF3SO2-, C2F5SO2-, C4F9SO2-, C6F13SO2- et C8F17SO2-) et les radicaux perfluoroalkyles ayant de 1 à 12 atomes de carbone (de préférence CF3-, C2F5-, C4F9-, C6F13-, C8F17- et C10F21-), et RF et R'F sont choisis indépendamment l'un de l'autre dans le groupe constitué par les groupements alkyles ayant de 1 à 10 atomes de carbone (de préférence par CF3-, C2F5-, C4F9-, C6F13-, C8F17-et C10F21-), ou RF et R'F forment ensemble un radical perfluoroalkylène linéaire divalent ayant de 1 à 8 atomes de carbone.Mention may also be made of the sulfonylmethylide anions [R F SO 2 C (Q) SO 2 R ′ F ] - in which Q is chosen from the group consisting of alkyl, aryl, alkylaryl or arylalkyl groups having at most 30 carbon atoms, perfluoroalkylsulfonyl groups having from 1 to 8 carbon atoms (preferably CF 3 SO 2 -, C 2 F 5 SO 2 -, C 4 F 9 SO 2 -, C 6 F 13 SO 2 - and C 8 F 17 SO 2 -) and perfluoroalkyl radicals having from 1 to 12 carbon atoms (preferably CF 3 -, C 2 F 5 -, C 4 F 9 -, C 6 F 13 -, C 8 F 17 - and C 10 F 21 - ), and R F and R ' F are chosen independently of each other from the group consisting of alkyl groups having from 1 to 10 carbon atoms (preferably by CF 3 -, C 2 F 5 -, C 4 F 9 -, C 6 F 13 -, C 8 F 17 - and C 10 F 21 -), where R F and R ' F together form a divalent linear perfluoroalkylene radical having from 1 to 8 carbon atoms.
Les anions [RFSO2NSO2R'F]- et [RFSO2C (SO2R"F) SO2R'F]- dans lesquels RF, R'F, et R"F représentent chacun un groupement perfluoroalkyle ayant de 1 à 10 atomes de carbone, de préférence de 1 à 6 atomes de carbone, sont particulièrement avantageux ainsi que les composés [RFCH2-O-SO2)2N]- et [(RF)2CH-O-SO2)2N]-.The anions [R F SO 2 NSO 2 R ' F ] - and [R F SO 2 C (SO 2 R " F ) SO 2 R' F ] - in which R F , R ' F , and R" F each represent a perfluoroalkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, are particularly advantageous as well as the compounds [R F CH 2 -O-SO 2 ) 2 N] - and [(R F ) 2 CH-O-SO 2 ) 2 N] - .
Une famille particulière de composés selon l'invention
comprend les sels de polyiodonium qui répondent à l'une
des formules suivantes (I), (II), (III) ou (IV) :
dans laquelle :
- les radicaux alkyles ou arylalkyles linéaires ou ramifiés ayant de 1 à 30 atomes de carbone ;
- les radicaux alkényles ayant de 1 à 30 atomes de carbone ;
- les radicaux aryles ou alkylaryles ayant de 6 à 30 atomes de carbone, incluant ceux qui ont des noyaux condensés ;
- les radicaux ayant de 1 à 30 atomes de carbone et choisis dans le groupe constitué par les oxaalkyles, les azaalkyles, les thiaalkyles, les phosphaalkyles, les oxaalkylènes, les azaalkylènes, les thiaalkylènes, les phosphaalkylènes,
- les radicaux ayant de 1 à 30 atomes de carbone et incluant un groupement sulfoxyde, un groupement sulfone, un groupement oxyde de phosphine, un groupement phosphonate, tous ces radicaux étant obtenus par addition d'oxygène sur les atomes de soufre ou de phosphore ;
- les radicaux hétérocycliques aromatiques ou alicycliques comprenant au moins un hétéroatome choisi dans le groupe constitué par O, N, S et P ;
- -NO, -CN, -OH, -Cl, -Br, -I, -F ;
- linear or branched alkyl or arylalkyl radicals having from 1 to 30 carbon atoms;
- alkenyl radicals having from 1 to 30 carbon atoms;
- aryl or alkylaryl radicals having from 6 to 30 carbon atoms, including those which have condensed nuclei;
- radicals having from 1 to 30 carbon atoms and chosen from the group consisting of oxaalkyls, azaalkyls, thiaalkyls, phosphaalkyls, oxaalkylenes, azaalkylenes, thiaalkylenes, phosphaalkylenes,
- radicals having from 1 to 30 carbon atoms and including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group, all these radicals being obtained by addition of oxygen to the sulfur or phosphorus atoms;
- aromatic or alicyclic heterocyclic radicals comprising at least one heteroatom chosen from the group consisting of O, N, S and P;
- -NO, -CN, -OH, -Cl, -Br, -I, -F;
Parmi les composés du type polyiodonium, on préfère tout particulièrement ceux dans lesquels les substituants R1n et R2n sont choisis indépendamment les uns des autres dans le groupe constitué par les radicaux alkyles linéaires ayant de 1 à 18 atomes de carbone, le 2-éthylhexyle, le phényle, les oxaalkyles répondant à la formule R-(OCH2CH2)y-ou R-[OCH(CH3)CH2]y- dans lesquels R est un radical alkyle linéaire ayant de 1 à 18 atomes de carbone et 1≤y≤22.Among the compounds of the polyiodonium type, very particularly preferred are those in which the substituents R 1n and R 2n are chosen independently of one another in the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2-ethylhexyl , phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y -or R- [OCH (CH 3 ) CH 2 ] y - in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1≤y≤22.
Lorsque le composé polyiodonium de l'invention répond à l'une des formules (I) ou (II), il se présente sous la forme d'un dimère ou d'un polymère comprenant les groupements ioniques iodonium dans la chaíne du polymère. When the polyiodonium compound of the invention responds in one of the formulas (I) or (II), it is presented under the form of a dimer or of a polymer comprising the Iodonium ionic groups in the polymer chain.
Lorsque le composé polyiodonium répond à l'une des formules (III) ou (IV), il se présente sous la forme d'un polymère dans lequel les groupements ioniques iodonium sont portés par des substituants pendants.When the polyiodonium compound meets one of the formulas (III) or (IV), it takes the form of a polymer in which the iodonium ionic groups are carried by pendant substituents.
Une autre famille particulière de composés selon
l'invention comprend les sels de polysulfonium qui
répondent à l'une des formules (V), (VI), (VII), (VIII) ou
(IX) suivantes :
dans laquelle :
- les radicaux alkyles ou arylalkyles linéaires ou ramifiés ayant de 1 à 30 atomes de carbone ;
- les radicaux alkényles ayant de 1 à 30 atomes de carbone ;
- les radicaux aryles ou alkylaryles ayant de 6 à 30 atomes de carbone, incluant ceux qui ont des noyaux condensés ;
- les radicaux ayant de 1 à 30 atomes de carbone et choisis dans le groupe constitué par les oxaalkyles, les azaalkyles, les thiaalkyles, les phosphaalkyles, les oxaalkylènes, les azaalkylènes, les thiaalkylènes, les phosphaalkylènes,
- les radicaux ayant de 1 à 30 atomes de carbone et incluant un groupement sulfoxyde, un groupement sulfone, un groupement oxyde de phosphine, un groupement phosphonate, tous ces radicaux étant obtenus par addition d'oxygène sur les atomes de soufre ou de phosphore ;
- les radicaux hétérocycliques aromatiques ou alicycliques comprenant au moins un hétéroatome choisi dans le groupe constitué par O, N, S et P ;
- -NO, -CN, -OH, -Cl, -Br, -I, -F ;
- linear or branched alkyl or arylalkyl radicals having from 1 to 30 carbon atoms;
- alkenyl radicals having from 1 to 30 carbon atoms;
- aryl or alkylaryl radicals having from 6 to 30 carbon atoms, including those which have condensed nuclei;
- radicals having from 1 to 30 carbon atoms and chosen from the group consisting of oxaalkyls, azaalkyls, thiaalkyls, phosphaalkyls, oxaalkylenes, azaalkylenes, thiaalkylenes, phosphaalkylenes,
- radicals having from 1 to 30 carbon atoms and including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group, all these radicals being obtained by addition of oxygen to the sulfur or phosphorus atoms;
- aromatic or alicyclic heterocyclic radicals comprising at least one heteroatom chosen from the group consisting of O, N, S and P;
- -NO, -CN, -OH, -Cl, -Br, -I, -F;
On préfère tout particulièrement les composés polysulfonium dans lesquels les substituants R1n, R3 et R4 sont choisis dans le groupe constitué par les radicaux alkyles linéaires ayant de 1 à 18 atomes de carbone, le 2éthylhexyle, le phényle, les oxaalkyles répondant à la formule R-(OCH2CH2)y- ou R- [OCH (CH3)CH2]y- dans lesquels R est un radical alkyle linéaire ayant de 1 à 18 atomes de carbone et 1≤y≤22.Particularly preferred are the polysulfonium compounds in which the substituents R 1n , R 3 and R 4 are chosen from the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2ethylhexyl, phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y - or R- [OCH (CH 3 ) CH 2 ] y - in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1≤y≤22.
Lorsqu'un composé polysulfonium de l'invention correspondant à la formule (V) est un dimère. Un composé polysulfonium répondant à l'une des formules (VII) ou (VIII) se présente sous la forme d'un polymère portant des groupements ioniques dans la chaíne principale.When a polysulfonium compound of the invention corresponding to formula (V) is a dimer. A compound polysulfonium corresponding to one of the formulas (VII) or (VIII) is in the form of a polymer bearing ionic groupings in the main chain.
Lorsqu'un composé polysulfonium répond à l'une des formules (VI) ou (IX), il se présente sous la forme d'un polymère sur lesquels les groupements ioniques sont portés par des groupements latéraux.When a polysulfonium compound meets one of the formulas (VI) or (IX), it takes the form of a polymer on which the ionic groups are carried by lateral groupings.
Une autre famille particulière de composés selon
l'invention comprend les sels de polyacylsulfonium qui
répondent à l'une des formules suivantes (X), (XI), (XII),
(XIII) ou (XIV) :
dans laquelle
Parmi les composés polyacylsulfonium, on préfère tout particulièrement ceux dans lesquels les substituants R1n, R5 et R6 sont choisis dans le groupe constitué par les radicaux alkyles linéaires ayant de 1 à 18 atomes de carbone, le 2-éthylhexyle, le phényle, les oxaalkyles répondant à la formule R-(OCH2CH2)y- ou R-[OCH(CH3)CH2]y-dans lesquels R est un radical alkyle linéaire ayant de 1 à 18 atomes de carbone et 1≤y≤22.Among the polyacylsulfonium compounds, very particularly preferred are those in which the substituents R 1n , R 5 and R 6 are chosen from the group consisting of linear alkyl radicals having from 1 to 18 carbon atoms, 2-ethylhexyl, phenyl, oxaalkyls corresponding to the formula R- (OCH 2 CH 2 ) y - or R- [OCH (CH 3 ) CH 2 ] y -in which R is a linear alkyl radical having from 1 to 18 carbon atoms and 1≤y ≤22.
Une quatrième famille de composés selon l'invention
comprend les sels de polydiazonium répondant à la formule
(XI)
dans laquelle
Une cinquième famille de composés selon l'invention
comprend les polyonium organométalliques répondant à l'une
des formules suivantes :
dans lesquelles
- les radicaux alkyles ou arylalkyles linéaires ou ramifiés ayant de 1 à 30 atomes de carbone ;
- les radicaux alkényles ayant de 1 à 30 atomes de carbone ;
- les radicaux aryles ou alkylaryles ayant de 6 à 30 atomes de carbone, incluant ceux qui ont des condensés ;
- les radicaux ayant de 1 à 30 atomes de carbone et choisis dans le groupe constitué par les oxaalkyles, les azaalkyles, les thiaalkyles, les phosphaalkyles, les oxaalkylènes, les azaalkylènes, les thiaalkylènes, les phosphaalkylènes,
- les radicaux ayant de 1 à 30 atomes de carbone et incluant un groupement sulfoxyde, un groupement sulfone, un groupement oxyde de phosphine, un groupement phosphonate, tous ces radicaux étant obtenus par addition d'oxygène sur les atomes de soufre ou de phosphore ;
- les radicaux hétérocycliques aromatiques ou alicycliques comprenant au moins un hétéroatome choisi dans le groupe constitué par O, N, S et P ;
- -NO, -CN, -OH, -Cl, -Br, -I, -F ;
- linear or branched alkyl or arylalkyl radicals having from 1 to 30 carbon atoms;
- alkenyl radicals having from 1 to 30 carbon atoms;
- aryl or alkylaryl radicals having from 6 to 30 carbon atoms, including those which have condensates;
- radicals having from 1 to 30 carbon atoms and chosen from the group consisting of oxaalkyls, azaalkyls, thiaalkyls, phosphaalkyls, oxaalkylenes, azaalkylenes, thiaalkylenes, phosphaalkylenes,
- radicals having from 1 to 30 carbon atoms and including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group, all these radicals being obtained by addition of oxygen to the sulfur or phosphorus atoms;
- aromatic or alicyclic heterocyclic radicals comprising at least one heteroatom chosen from the group consisting of O, N, S and P;
- -NO, -CN, -OH, -Cl, -Br, -I, -F;
Comme exemples de composés dans lesquels la partie cationique est un polycation organométallique, on peut citer les polymères contenant les unités ferrocénium, (en particulier ceux qui incorporent l'unité vinylférrocène, les unités polyalkylbenzène-fer-cyclopentadiène), les polymères qui incorporent des unités nickelocènium, et les polymères qui incorporent des unités tricarbonyl manganèsecyclopentadiène.As examples of compounds in which the part cationic is an organometallic polycation, we can cite the polymers containing the ferrocenium units, (in especially those which incorporate the vinylferrocene unit, polyalkylbenzene-iron-cyclopentadiene units), polymers which incorporate nickelocenium units, and polymers that incorporate tricarbonyl units manganesecyclopentadiene.
Les composés (A+X-)p de la présente invention sont en général insolubles dans l'eau. Ils peuvent donc être préparés par un procédé consistant à effectuer une métathèse dans l'eau ou un mélange eau/alcool léger (méthanol, éthanol, propanol) entre composé (A+X1 -)p qui est un sel soluble du polycation (A+)p dans lequel l'anion X1 - a un caractère hydrophile, et un composé soluble dans l'eau de l'anion X- ayant cation fortement hydrophile.The compounds (A + X - ) p of the present invention are generally insoluble in water. They can therefore be prepared by a process consisting in carrying out a metathesis in water or a water / light alcohol mixture (methanol, ethanol, propanol) between compound (A + X 1 - ) p which is a soluble salt of the polycation (A + ) p in which the anion X 1 - has a hydrophilic character, and a water-soluble compound of the anion X - having a highly hydrophilic cation.
Les sels solubles (A+X1 -)p du polycation (A+)p sont choisis de préférence parmi les sels dans lesquels l'anion X1 - est choisi parmi un hydroxyde, un chlorure, un bromure, un hydrogénosulfate, un dihydrogénophosphate ou un méthylsulfonate. Ces anions étant fortement solvatés par l'eau ou les alcools légers, ils favorisent la solubilité.The soluble salts (A + X 1 - ) p of the polycation (A + ) p are preferably chosen from the salts in which the anion X 1 - is chosen from a hydroxide, a chloride, a bromide, a hydrogen sulphate, a dihydrogen phosphate or a methylsulfonate. These anions being strongly solvated by water or light alcohols, they promote solubility.
Les composés solubles dans l'eau ou les mélanges eau/alcools de l'anion X- sont choisis de préférence parmi les perhaloalkylsulfonimides et les perhaloalkylsulfonyl-méthanes, les perhaloalkylsulfonimidures et les perhaloalkylsulfonylméthylures de lithium, de sodium, de potassium, d'ammonium, de calcium ou de magnésium. Le choix du cation dépend bien entendu de la facilité d'obtention et du minimum d'hydrophilie requise pour entraíner la solubilité.The water-soluble compounds or the water / alcohol mixtures of the anion X - are preferably chosen from perhaloalkylsulfonimides and perhaloalkylsulfonyl-methanes, perhaloalkylsulfonimides and perhaloalkylsulfonylmethylides of lithium, sodium, potassium, ammonium, calcium or magnesium. The choice of cation depends of course on the ease of obtaining and the minimum hydrophilicity required to cause the solubility.
Lorsque le composé polyionique (A+X-)p de l'invention est préparé à partir d'un sel (A+X1 -)p dans lequel X1 est un chlorure, un bromure, un alkylsulfonate, un alkyloxy-sulfonate ou un arylsulfonate, dont les sels de Na ou de K sont insolubles dans les solvant usuels, il est avantageux de conduire la réaction en présence d'un sel de Na ou K de l'anions X-. La solubilité de ces sels dans les solvants même de moyenne polarité étant appréciable, les sels insolubles tel que NaCl, Kbr précipitent alors que le composé polyionique de l'invention reste en solution. Comme solvants, on peut citer l'acétone, le méthyléthylcétone, l'acétonitrile, le THF, les esters tels que les formiates ou l'acétate de méthyle ou d'éthyle.When the polyionic compound (A + X - ) p of the invention is prepared from a salt (A + X 1 - ) p in which X 1 is a chloride, a bromide, an alkylsulfonate, an alkyloxy-sulfonate or an arylsulfonate, the salts of Na or K of which are insoluble in the usual solvents, it is advantageous to carry out the reaction in the presence of a salt of Na or K of the anions X - . The solubility of these salts in solvents even of medium polarity being appreciable, the insoluble salts such as NaCl, Kbr precipitate while the polyionic compound of the invention remains in solution. As solvents, mention may be made of acetone, methyl ethyl ketone, acetonitrile, THF, esters such as formates or methyl or ethyl acetate.
Il faut noter que tout autre procédé d'échange ionique peut être mis en oeuvre, par exemple un procédé utilisant une résine échangeuse d'ions, ou un procédé de précipitation sélective.It should be noted that any other ion exchange process can be implemented, for example a method using an ion exchange resin, or a method of selective precipitation.
De manière surprenante, il est apparu que les composés polyioniques de l'invention sont solubles dans la plupart des solvants organiques usuels, contrairement à des composés polyioniques de l'art antérieur tels que les polystyrène-iodoniumn les poly thiaphénylsulfonium malgré une densité de charge élévée. Ces derniers ne sont solubles que dans l'eau et les solvants très polaires tels que la diméthylformamide (DMF) ou le carbonate de propylène suivant le type de contre ion. Or l'eau est incompatible, avec les réactions de polymérisation cationique et n'est pas un solvant de la plupart des monomères. Les solvants tels la DMF ou le carbonate de propylène sont très difficiles à éliminer du fait de leur température d'ébullition élevée et ils peuvent ultérieurement contaminer les matières en contact avec les produits de la polymérisation/réticulation (industrie alimentaire, sérigraphies...). Les polycations de l'invention ont dès lors pu être utilisés comme photoamorceurs pour des réactions de polymérisation cationique. Par rapport aux composés monomères ioniques, ils présentent un avantage certain : lorsqu'ils sont utilisés comme photoamorceurs, ils se décomposent sous l'action du rayonnement actinique sans laisser de résidus suceptibles de migrer dans la phase polymérique obtenue.Surprisingly, it appeared that the compounds polyionics of the invention are soluble in most usual organic solvents, unlike polyionic compounds of the prior art such as polystyrene-iodonium poly thiaphenylsulfonium despite a high charge density. These are only soluble in water and very polar solvents such as dimethylformamide (DMF) or propylene carbonate depending on the type of counter ion. Water is incompatible, with cationic polymerization reactions and is not not a solvent for most monomers. Solvents such as DMF or propylene carbonate are very difficult to remove due to their temperature high boiling point and they can later contaminate the materials in contact with the products of the polymerization / crosslinking (food industry, serigraphs ...). The polycations of the invention therefore have could be used as photoinitiators for cationic polymerization. Compared to compounds ionic monomers, they have a certain advantage: when used as photoinitiators, they decompose under the action of actinic radiation without leave residue likely to migrate into the phase polymer obtained.
La présente invention a par conséquent pour objet l'utilisation des composés polyioniques (A+X-)p de l'invention comme photoamorceurs sources d'acides de Brønsted catalyseurs de polymérisation ou de réticulation de monomères ou de prépolymères capables de réagir par voie cationique, ou catalyseurs pour la modification des paramètres de solubilité de polymères. Le procédé de polymérisation ou de réticulation de monomères ou de prépolymères capables de réagir par voie cationique est caractérisé en ce que l'on utilise un composé de l'invention comme photoamorceur source d'acide catalysant la réaction de polymérisation.The present invention therefore relates to the use of the polyionic compounds (A + X - ) p of the invention as photoinitiators sources of Brønsted acids catalysts for polymerization or crosslinking of monomers or prepolymers capable of reacting cationically , or catalysts for modifying the solubility parameters of polymers. The process for the polymerization or crosslinking of monomers or prepolymers capable of reacting cationically is characterized in that a compound of the invention is used as photoinitiator source of acid catalyzing the polymerization reaction.
Lorsque le composé polyionique de l'invention est destiné à être utilisé comme photoamorceur pour la polymérisation de monomères ou de prépolymères polymérisant par voie cationique, le choix des groupements R1 à R8 est effectué parmi les radicaux ci-dessus pour augmenter la solubilité dudit composé dans les solvants de mise en oeuvre des monomères ou des prépolymères et en fonction des propriétés souhaitées pour le polymère final. Par exemple, le choix de radicaux alkyles non substitués donne une solubilité dans les milieux peu polaires. Le choix de radicaux comprenant un groupe oxa ou une sulfone donnera une solubilité dans les milieux polaires. Les radicaux incluant un groupement sulfoxyde, un groupement sulfone, un groupement oxyde de phosphine, un groupement phosphonate obtenu par addition d'oxygène sur les atomes de soufre ou de phosphore peuvent conférer au polymère obtenu des propriétés améliorées en ce qui concerne l'adhésion, la brillance, la résistance à l'oxydation ou aux UV.When the polyionic compound of the invention is intended to be used as a photoinitiator for the polymerization of monomers or prepolymers polymerizing cationically, the choice of groups R 1 to R 8 is made from the above radicals to increase the solubility of said compound in the solvents used for the monomers or prepolymers and according to the properties desired for the final polymer. For example, the choice of unsubstituted alkyl radicals gives solubility in slightly polar media. The choice of radicals comprising an oxa group or a sulfone will give solubility in polar media. The radicals including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group obtained by adding oxygen to the sulfur or phosphorus atoms can confer on the polymer obtained improved properties with regard to adhesion, shine, resistance to oxidation or UV.
Les monomères et les prépolymères qui peuvent être polymérisés ou réticulés à l'aide des photoamorceurs polyioniques de la présente invention sont ceux qui peuvent subir une polymérisation cationique.The monomers and prepolymers which can be polymerized or crosslinked using photoinitiators polyionics of the present invention are those which can undergo cationic polymerization.
Parmi les monomères qui peuvent être polymérisés ou réticulés à l'aide d'un composé polyionique de l'invention utilisé comme photoamorceur, on peut citer les monomères qui comportent une fonction éther cyclique, une fonction thioéther cyclique ou une fonction amine cyclique les composés vinyliques, (plus particulièrement les éthers vinyliques), les oxazolines, les lactones et les lactames.Among the monomers which can be polymerized or crosslinked using a polyionic compound of the invention used as photoinitiator, mention may be made of the monomers which have a cyclic ether function, a function cyclic thioether or a cyclic amine function them vinyl compounds, (more particularly ethers vinyl), oxazolines, lactones and lactams.
Parmi les monomères du type éther ou thioéther cyclique, on peut citer l'oxyde d'éthylène, l'oxyde de propylène, l'oxétane, l'épichlorhydrine, le tétrahydrofurane, l'oxyde de styrène, l'oxyde de cyclohexène, l'oxyde de vinylcyclohexène, le glycidol, l'oxyde de butylène, l'oxyde d'octylène, les éthers et les esters de glycidyle (par exemple le méthacrylate ou l'acrylate de glycidyle, le phényl glycidyl éther, le diglycidyléther de bisphénol A ou ses dérivés fluorés), les acétals cycliques ayant de 4 à 15 atomes de carbone (par exemple le dioxolane, le 1,3-dioxane, le 1,3-dioxépane).Among the monomers of the ether or thioether type cyclic, mention may be made of ethylene oxide, propylene, oxetane, epichlorohydrin, tetrahydrofuran, styrene oxide, cyclohexene oxide, oxide vinylcyclohexene, glycidol, butylene oxide, octylene oxide, glycidyl ethers and esters (e.g. methacrylate or glycidyl acrylate, phenyl glycidyl ether, diglycidyl ether of bisphenol A or its fluorinated derivatives), cyclic acetals having from 4 to 15 carbon atoms (e.g. dioxolane, 1,3-dioxane, 1,3-dioxepane).
Parmi les composés vinyliques, les éthers vinyliques constituent une famille très importante de monomères sensibles en polymérisation cationique. A titre d'exemple, on peut citer l'éthyl vinyl éther, le propyl vinyl éther, l'isobutyl vinyl éther, l'octadécyl vinyl éther, l'éthylèneglycol monovinyl éther, le diéthylèneglycol divinyl éther, le butanediol monovinyl éther, le butanediol divinyl éther, l'hexanediol divinyl éther, l'éthylèneglycol butyl vinyl éther, le triéthylèneglycol méthyl vinyl éther, le cyclohexanediméthano monovinyl éther, le cyclohexane-diméthanol divinyl éther, le 2-éthylhexyl vinyl éther, le poly-THF-divinyl éther ayant une masse comprise entre 150 et 5000, le diéthylèneglycol monovinyl éther, le triméthylolpropane trivinyl éther, l'aminopropyl vinyl éther, le 2-diéthylaminoéthyl vinyl éther.Among vinyl compounds, vinyl ethers constitute a very important family of monomers sensitive in cationic polymerization. For exemple, mention may be made of ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, butanediol monovinyl ether, butanediol divinyl ether, hexanediol divinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, cyclohexanedimethano monovinyl ether, cyclohexane-dimethanol divinyl ether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether having a mass between 150 and 5000, diethylene glycol monovinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether.
On peut également citer les éthers méthyl-vinyliques qui contiennent un ou plusieurs groupements CH3CH=CH-O- et qui sont avantageusement obtenus par isomérisation des éthers allyliques correspondants en présence d'un catalyseur tel que (Φ3P)2RuCl2.Mention may also be made of methyl vinyl ethers which contain one or more groups CH3CH = CH-O- and which are advantageously obtained by isomerization of the corresponding allyl ethers in the presence of a catalyst such as (Φ 3 P) 2RuCl 2 .
Comme autres composés vinyliques qui peuvent être soumis à une polymérisation cationique en présence d'un composé polyionique de l'invention utilisé en tant que photoamorceur, on peut citer à titre d'exemple les 1,1dialkyléthylènes (par exemple l'isobutène), les monomères aromatiques vinyliques (par exemple le styrène, les αalkylstyrène, notamment l'α-méthylstyrène, le 4vinylanisole, l'acénaphtène), les composés N-vinyliques (par exemple la N-vinylpyrolidone, le N-vinyl formamide ou les N-vinyl sulfonamides).As other vinyl compounds which can be subjected to cationic polymerization in the presence of a polyionic compound of the invention used as photoinitiator, mention may be made, for example, of 1,1dialkylethylenes (e.g. isobutene), monomers vinyl aromatics (for example styrene, αalkylstyrene, in particular α-methylstyrene, 4vinylanisole, acenaphthene), N-vinyl compounds (for example N-vinylpyrolidone, N-vinyl formamide or N-vinyl sulfonamides).
Parmi les prépolymères, on peut citer les composés dans lesquels des groupements époxy sont portés par une chaíne aliphatique, une chaíne aromatique, ou une chaíne hétérocyclique, par exemple les éthers glycidiques du bisphénol A éthoxylés par 3 à 15 unités d'oxyde d'éthylène ou de propylène, les siloxanes possédant des groupements latéraux du type époxycyclohexène-éthyle obtenus par hydrosilylation des copolymères de di alkyl, d'alkylaryle ou de diaryl siloxane avec le méthyl hydrogénosiloxane en présence d'oxyde de vinylcyclohexène, ou d'éthers insaturés difonctionnels possédant une extrémité vinyléther et une extrémité méthylvinyléther (propènyl), les produits de condensation du type sol-gel obtenus à partir du triéthoxy ou du triméthoxy silapropylcyclohexène oxyde, les uréthanes incorporant les produits de réaction du butanediol monovinyléther et d'un alcool de fonctionnalité supérieure ou égale à 2 sur un di ou un tri isocyanate aliphatique ou aromatique. Among the prepolymers, mention may be made of the compounds in which epoxy groups are carried by a aliphatic chain, an aromatic chain, or a chain heterocyclic, for example the glycidic ethers of bisphenol A ethoxylated with 3 to 15 units of ethylene oxide or propylene, the siloxanes having groups side of the epoxycyclohexene-ethyl type obtained by hydrosilylation of di alkyl, alkylaryl copolymers or diaryl siloxane with methyl hydrogen siloxane in presence of vinylcyclohexene oxide, or of unsaturated ethers difunctionals having a vinyl ether end and a methylvinyl ether (propenyl) end, the products of sol-gel type condensation obtained from triethoxy or trimethoxy silapropylcyclohexene oxide, urethanes incorporating butanediol reaction products monovinyl ether and a higher functionality alcohol or equal to 2 on an aliphatic di or tri isocyanate or aromatic.
Le procédé de polymérisation selon l'invention consiste à mélanger au moins un monomère ou prépolymère capable de polymériser par voie cationique et au moins un composé polyionique (A+X-)p de l'invention, et à soumettre le mélange obtenu à un rayonnement actinique ou un rayonnement β. De préférence, le mélange réactionnel est soumis au rayonnement après avoir été mis sous forme d'une couche mince ayant une épaisseur inférieure à 5 mm, de préférence sous forme d'un film mince ayant une épaisseur inférieure ou égale à 500 µm. La durée de la réaction dépend de l'épaisseur de l'échantillon et de la puissance de la source à la longueur d'onde λ active. Elle est définie par la vitesse de défilement devant la source, qui est comprise entre 300 m/min et 1 cm/min. Des couches de matériau final ayant une épaisseur supérieure à 5 mm peuvent être obtenues en répétant plusieurs fois l'opération consistant à épandre une couche et à la traiter par le rayonnement.The polymerization process according to the invention consists in mixing at least one monomer or prepolymer capable of polymerizing cationically and at least one polyionic compound (A + X - ) p of the invention, and in subjecting the mixture obtained to radiation actinic or β radiation. Preferably, the reaction mixture is subjected to radiation after having been formed in the form of a thin layer having a thickness less than 5 mm, preferably in the form of a thin film having a thickness less than or equal to 500 μm. The reaction time depends on the thickness of the sample and the power of the source at the active wavelength λ. It is defined by the speed of travel in front of the source, which is between 300 m / min and 1 cm / min. Layers of final material having a thickness greater than 5 mm can be obtained by repeating several times the operation of spreading a layer and treating it with radiation.
Généralement, la quantité de photoamorceur polyionique (A+X-)p utilisé est comprise entre 0,01 et 15 % en poids par rapport au poids de monomère ou de prépolymère, de préférence entre 0,1 et 5 % en poids.Generally, the amount of polyionic photoinitiator (A + X - ) p used is between 0.01 and 15% by weight relative to the weight of monomer or prepolymer, preferably between 0.1 and 5% by weight.
Un composé polyionique (A+X-)p de la présente invention peut être utilisé comme photoamorceur en l'absence de solvant, notamment lorsque l'on souhaite polymériser des monomères liquides dans lesquels le sel est soluble ou aisément dispersable. Cette forme d'utilisation est particulièrement intéressante, car elle permet de supprimer les problèmes liés aux solvants (toxicité, inflammabilité).A polyionic compound (A + X - ) p of the present invention can be used as photoinitiator in the absence of solvent, especially when it is desired to polymerize liquid monomers in which the salt is soluble or easily dispersible. This form of use is particularly interesting, because it eliminates the problems associated with solvents (toxicity, flammability).
Un composé polyionique (A+X-)p de la présente invention peut également être utilisé en tant que photoamorceur sous forme d'une solution homogène dans un solvant inerte vis-à-vis de la polymérisation, prête à l'emploi et aisément dispersable, en particulier dans le cas où le milieu à polymériser ou à réticuler présente une viscosité élevée.A polyionic compound (A + X - ) p of the present invention can also be used as a photoinitiator in the form of a homogeneous solution in a solvent inert to the polymerization, ready to use and easily dispersible , in particular in the case where the medium to be polymerized or to be crosslinked has a high viscosity.
Comme exemple de solvant inerte, on peut citer les solvants volatils, tels que l'acétone, la méthyl-éthyl cétone et l'acétonitrile. Ces solvants serviront simplement à diluer les produits à polymériser ou à réticuler (pour les rendre moins visqueux, surtout lorsqu'il s'agit d'un prépolymère). Ils seront éliminés après la polymérisation ou la réticulation par séchage. On peut également citer les solvants non volatils. Un solvant non volatil sert de la même manière qu'un solvant volatil, à diluer les produits que l'on veut polymériser ou réticuler, et à dissoudre le composé polyionique) (A+X-)p de l'invention utilisé comme photoamorceur, mais en outre il restera dans le matériau formé et il agira ainsi comme plastifiant. A titre d'exemple, on peut citer le carbonate de propylène, la γbutyrolactone, les éther-esters des mono-, di-, triéthylène ou propylène glycols, les éther-alcools des mono-, di-, tri- éthylène ou propylène glycols, les plastifiants tels que les esters de l'acide phtalique ou de l'acide citrique.As an example of an inert solvent, there may be mentioned volatile solvents, such as acetone, methyl ethyl ketone and acetonitrile. These solvents will simply serve to dilute the products to be polymerized or crosslinked (to make them less viscous, especially when it is a prepolymer). They will be removed after polymerization or crosslinking by drying. Mention may also be made of non-volatile solvents. A non-volatile solvent is used in the same way as a volatile solvent, to dilute the products which it is desired to polymerize or crosslink, and to dissolve the polyionic compound) (A + X - ) p of the invention used as photoinitiator, but in addition it will remain in the material formed and it will thus act as a plasticizer. By way of example, mention may be made of propylene carbonate, γbutyrolactone, ether-esters of mono-, di-, triethylene or propylene glycols, ether-alcohols of mono-, di-, tri-ethylene or propylene glycols , plasticizers such as esters of phthalic acid or citric acid.
Dans un autre mode de mise en oeuvre de l'invention, on utilise comme solvant ou diluant un composé réactif vis-à-vis de la polymérisation, qui est un composé de faible masse moléculaire et de faible viscosité qui va jouer à la fois le rôle de monomère polymérisable et le rôle de solvant ou de diluant pour des monomères plus visqueux ou des prépolymères utilisés conjointement. Après la réaction, ces monomères ayant servi de solvant font partie du réseau macromoléculaire finalement obtenu, leur intégration étant plus grande lorsqu'il s'agit de monomères bi-fonctionnels. Le matériau obtenu après irradiation ne contient plus de produits ayant un faible poids moléculaire et une tension de vapeur appréciable, ou susceptibles de contaminer les objets avec lesquels le polymère est en contact. A titre d'exemple, un solvant réactif peut être choisi parmi les mono et di éthers vinyliques des mono-, di-, tri-, tétraéthylène et propylène glycols, la N-méthylpyrolidone, le 2propényléther du carbonate de propylène commercialisé par exemple sous la dénomination PEPC par la société ISP, New Jersey, Etats-Unis.In another embodiment of the invention, a reactive compound vis-à-vis is used as solvent or diluent of polymerization, which is a compound of low molecular mass and low viscosity which will play the both the role of polymerizable monomer and the role of solvent or diluent for more viscous monomers or prepolymers used together. After the reaction, these monomers having served as solvent are part of the network macromolecular finally obtained, their integration being greater in the case of bi-functional monomers. The material obtained after irradiation no longer contains products with low molecular weight and tension appreciable vapor, or likely to contaminate objects with which the polymer is in contact. As for example, a reactive solvent can be chosen from mono and di vinyl ethers of mono-, di-, tri-, tetraethylene and propylene glycols, N-methylpyrolidone, 2propenylether propylene carbonate marketed by example under the name PEPC by the company ISP, New Jersey, United States.
Pour irradier le mélange réactionnel, le rayonnement peut être choisi parmi le rayonnement ultraviolet, le rayonnement visible, les rayons X, les rayons γ et le rayonnement β. Lorsque l'on utilise la lumière ultraviolette comme rayonnement actinique, il peut être avantageux d'ajouter aux photoamorceurs de l'invention des photosensibilisateurs destinés à permettre une photolyse efficace avec les longueurs d'ondes moins énergétiques que celles correspondant au maximum d'absorption du photoamorceur, telles que celles émises par les dispositifs industriels, (λ ≈ 300 nm pour les lampes à vapeur de mercure en particulier). De tels additifs sont connus, et à titre d'exemples non limitatifs, on peut citer l'anthracène, le diphényl-9,10-anthracène, le pérylène, la phénothiazine, le tétracène, la xanthone, la thioxanthone, l'acétophénone, la benzophénone, les 1,3,5-triaryl-2pyrazolines et leurs dérivés, en particulier les dérivés de substitution sur les noyaux aromatiques par des radicaux alkyles, oxa- ou aza-alkyles permettant entre autre de changer la longueur d'onde d'absorption. L'isopropylthioxantone est un exemple de photosensibilisateur préféré lorsque l'on utilise un composé polyiodonium Ap+pX- selon l'invention comme photoamorceur.To irradiate the reaction mixture, the radiation can be chosen from ultraviolet radiation, visible radiation, X-rays, γ rays and β radiation. When using ultraviolet light as actinic radiation, it may be advantageous to add to the photoinitiators of the invention photosensitizers intended to allow efficient photolysis with wavelengths less energetic than those corresponding to the maximum absorption of the photoinitiator, such as those emitted by industrial devices, (λ ≈ 300 nm for mercury vapor lamps in particular). Such additives are known, and by way of nonlimiting examples, mention may be made of anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine, tetracene, xanthone, thioxanthone, acetophenone, benzophenone, 1,3,5-triaryl-2pyrazolines and their derivatives, in particular the derivatives of substitution on the aromatic nuclei by alkyl, oxa- or aza-alkyl radicals allowing among others to change the wavelength of absorption. Isopropylthioxantone is an example of a preferred photosensitizer when a polyiodonium compound A p + pX - according to the invention is used as a photoinitiator.
Parmi les différents types de rayonnement mentionnés, le rayonnement ultraviolet est particulière préféré. D'une part, il est plus commode d'emploi que les autres rayonnements mentionnés. D'autre part, les photoamorceurs sont en général directement sensibles aux rayons UV et les photosensibilisateurs sont d'autant plus efficaces que la différence d'énergie (δλ) est plus faible.Among the different types of radiation mentioned, ultraviolet radiation is particularly preferred. Of a hand it is more convenient to use than the others radiation mentioned. On the other hand, photoinitiators are generally directly sensitive to UV rays and photosensitizers are all the more effective as the energy difference (δλ) is lower.
Les composés polyioniques (A+X-)p de l'invention peuvent aussi être mis en oeuvre en association avec des amorceurs de type radicalaire générés thermiquement ou par action d'une radiation actinique. Il est ainsi possible de polymériser ou de réticuler des mélanges de monomères ou de prépolymères contenant des fonctions dont les modes de polymérisation sont différents, par exemple des monomères ou des prépolymères polymérisant par voie radicalaire et des monomères ou des prépolymères polymérisant par voie cationique. Cette possibilité est particulièrement avantageuse pour créer des réseaux interpénétrés ayant des propriétés physiques différentes de celles qui seraient obtenues par simple mélange des polymères issus des monomères correspondants. Les éthers vinyliques ne sont pas ou sont peu actifs par amorçage radicalaire. Il est donc possible, dans un mélange réactionnel contenant un photoamorceur selon l'invention, un amorceur radicalaire, au moins un monomère du type éther vinylique et au moins un monomère comprenant des doubles liaisons non activées telles que celles des groupes allyliques, d'effectuer une polymérisation séparée de chaque type de monomère. Il est par contre connu que les monomères déficients en électrons, tels que les esters ou les amides de l'acide fumarique, de l'acide maléique, de l'acide acrylique ou méthacrylique, de l'acide itaconique, de l'acrylonitrile, du méthacrylonitrile, la maléimide et ses dérivés, forment en présence d'éthers vinyliques riches en électrons, des complexes de transfert de charge donnant des polymères alternés 1:1 par amorçage radicalaire. Un excès initial de monomères vinyliques par rapport à cette stoechiométrie permet de préserver des fonctions polymérisables par initiation cationique pure. Le déclenchement de l'activité d'un mélange d'amorceur radicalaire et d'amorceur cationique selon l'invention peut être fait simultanément pour les deux réactifs dans le cas par exemple d'insolation par un rayonnement actinique d'une longueur d'onde pour laquelle les photoamorceurs de l'invention et les amorceurs radicalaires choisis sont actifs, par exemple à λ = 250 nm. A titre d'exemple, on peut citer comme amorceurs les produits commerciaux suivants : Irgacure 184®, Irgacure 651®, Irgacure 261® Quantacure DMB®, Quantacure ITX®.The polyionic compounds (A + X - ) p of the invention can also be used in combination with initiators of the radical type generated thermally or by the action of actinic radiation. It is thus possible to polymerize or crosslink mixtures of monomers or prepolymers containing functions whose polymerization modes are different, for example monomers or prepolymers polymerizing by the radical route and monomers or prepolymers polymerizing by the cationic route. This possibility is particularly advantageous for creating interpenetrating networks having physical properties different from those which would be obtained by simple mixing of the polymers derived from the corresponding monomers. The vinyl ethers are not or are not very active by radical initiation. It is therefore possible, in a reaction mixture containing a photoinitiator according to the invention, a radical initiator, at least one monomer of the vinyl ether type and at least one monomer comprising non-activated double bonds such as those of the allylic groups, to carry out separate polymerization of each type of monomer. On the other hand, it is known that the electron-deficient monomers, such as the esters or the amides of fumaric acid, of maleic acid, of acrylic or methacrylic acid, of itaconic acid, of acrylonitrile, methacrylonitrile, maleimide and its derivatives, form, in the presence of vinyl ethers rich in electrons, charge transfer complexes giving alternating polymers 1: 1 by radical initiation. An initial excess of vinyl monomers with respect to this stoichiometry makes it possible to preserve polymerizable functions by pure cationic initiation. The triggering of the activity of a mixture of radical initiator and cationic initiator according to the invention can be done simultaneously for the two reagents in the case for example of exposure by actinic radiation of a wavelength for which the photoinitiators of the invention and the radical initiators chosen are active, for example at λ = 250 nm. By way of example, the following commercial products may be mentioned as initiators: Irgacure 184®, Irgacure 651®, Irgacure 261® Quantacure DMB®, Quantacure ITX®.
Il peut aussi être avantageux d'utiliser les deux modes de polymérisation d'une manière séquentielle, pour former dans un premier temps des prépolymères dont la mise en forme est aisée et dont le durcissement, l'adhésion, la solubilité ainsi que le degré de réticulation peuvent être modifiés par le déclenchement de l'activité de l'amorceur cationique. Par exemple, un mélange d'un amorceur radicalaire thermodissociable et d'un photoamorceur cationique selon l'invention permet de réaliser des polymérisations ou des réticulations séquentielles, d'abord sous l'action de la chaleur, puis sous l'action d'un rayonnement actinique. D'une manière similaire, si l'on choisit un amorceur radicalaire et un photoamorceur cationique selon l'invention, le premier étant photosensible à des longueurs d'ondes plus longues que celle déclenchant le photoamorceur selon l'invention, on obtient une réticulation en deux étapes contrôlables. Des amorceurs radicalaires peuvent être par exemple Irgacure® 651 permettant d'amorcer des polymérisations radicalaires à des longueurs d'onde de 365 nm.It may also be beneficial to use both polymerization modes in a sequential manner, for initially form prepolymers whose setting in shape is easy and whose hardening, adhesion, solubility as well as the degree of crosslinking can be modified by the initiation of the initiator activity cationic. For example, a mixture of a radical initiator heat dissociable and a cationic photoinitiator according to the invention makes it possible to carry out polymerizations or sequential cross-links, first under the action of heat, then under the action of actinic radiation. Similarly, if you choose a bait radical and a cationic photoinitiator according to the invention, the first being photosensitive to lengths longer waves than the one triggering the photoinitiator according to the invention, a crosslinking in two is obtained controllable steps. Radical initiators can be for example Irgacure® 651 allowing priming of radical polymerizations at wavelengths 365 nm.
L'invention a également pour objet l'utilisation des composés polyioniques (A+X-)p de l'invention pour les réactions d'amplification chimique de photoresists pour la microlithographie. Lors d'une telle utilisation, un film d'un matériau comprenant un polymère et un composé polyionique (A+X-)p de l'invention est soumis à une irradiation. L'irradiation provoque la formation de l'acide HX, qui catalyse la décomposition ou la transformation du polymère. Après décomposition ou transformation du polymère sur les parties du film qui ont été irradiées, les monomères formés ou le polymère transformé sont éliminés et il reste une image des parties non exposées. Pour cette application particulière, il est avantageux d'utiliser des composés polymères comprenant des unités vinyles portant un substituant ionique. Parmi ces composés, on peut citer les sels de polyiodonium répondant à la formule (III), les sels de polysulfonium répondant à la formule (VI), les polyacylsulfonium répondant à la formule (XI), les polydiazonium répondant à la formule (XV), les sels de complexes organométalliques répondant à la formule (XVIII). Ces composés permettent d'obtenir après photolyse des produits qui ne sont pas volatils, et donc pas odorants lorsqu'il s'agit de sulfures. Parmi les composés de l'invention, on préfère tout particulièrement les polysulfonium qui sont particulièrement efficaces comme photoamorceur, les phénacylsulfonium et les polymères et copolymères de vinyl ferrocénium qui peuvent être obtenus facilement. Parmi les polymères qui peuvent ainsi être modifiés en présence d'un composé de l'invention, on peut citer notamment les polymères contenant des motifs ester ou des motifs aryléther d'alcool tertiaire, par exemple les poly(phtalaldéhydes), les polymères de bisphénol A et d'un diacide, le polytertiobutoxycarbonyl oxystyrène, le polytertiobutoxy-a-méthyl styrène, le polyditertiobutylfumarate-co-allyltriméthylsilane et les polyacrylates d'un alcool tertiaire, en particulier le polyacrylate de tertiobutyle. D'autres polymères sont décrits dans J.V. Crivello et al, Chemistry of Materials 8, 376-381, (1996).A subject of the invention is also the use of the polyionic compounds (A + X - ) p of the invention for the chemical amplification reactions of photoresists for microlithography. During such use, a film of a material comprising a polymer and a polyionic compound (A + X - ) p of the invention is subjected to irradiation. The irradiation causes the formation of HX acid, which catalyzes the decomposition or transformation of the polymer. After decomposition or transformation of the polymer on the parts of the film which have been irradiated, the monomers formed or the transformed polymer are eliminated and an image of the unexposed parts remains. For this particular application, it is advantageous to use polymer compounds comprising vinyl units carrying an ionic substituent. Among these compounds, there may be mentioned the polyiodonium salts corresponding to formula (III), the polysulfonium salts corresponding to formula (VI), the polyacylsulfonium corresponding to formula (XI), the polydiazonium corresponding to formula (XV) , the salts of organometallic complexes corresponding to formula (XVIII). These compounds make it possible to obtain, after photolysis, products which are not volatile and therefore not odorous when it is a question of sulphides. Among the compounds of the invention, very particularly preferred are the polysulfonium which are particularly effective as a photoinitiator, the phenacylsulfonium and the polymers and copolymers of vinyl ferrocenium which can be obtained easily. Among the polymers which can thus be modified in the presence of a compound of the invention, mention may in particular be made of polymers containing ester units or aryl ether units of tertiary alcohol, for example poly (phthalaldehydes), bisphenol polymers A and a diacid, polytertiobutoxycarbonyl oxystyrene, polytertiobutoxy-a-methyl styrene, polyditertiobutylfumarate-co-allyltrimethylsilane and polyacrylates of a tertiary alcohol, in particular tertiary butyl polyacrylate. Other polymers are described in JV Crivello et al, Chemistry of Materials 8, 376-381, (1996).
Les composés polyioniques (A+X-)p de la présente invention, qui présentent une grande stabilité thermique, offrent de nombreux avantages par rapport aux sels connus de l'art antérieur. Ils ont des vitesses d'amorçage et de propagation comparables ou supérieures à celles obtenues à l'aide des anions de coordination de type PF6 -, AsF6 - et surtout SbF6 -. Les sels M+X- dans lesquels M est un métal alcalin et X un anion identique à l'anion d'un composé de la présente invention sont connus pour être facilement solvatés dans les polymères, dont ils augmentent peu la température de transition vitreuse. En outre, le coefficient de diffusion de l'anion X- est supérieur à celui des anions hexafluorométallates ou des anions tétrafluoroborates ou des anions phénylborates. Ces propriétés sont expliquées par la délocalisation de la charge négative et la flexibilité de l'anion autour des liaisons SNS ou SCS.The polyionic compounds (A + X - ) p of the present invention, which exhibit high thermal stability, offer numerous advantages over the salts known from the prior art. They have priming and propagation speeds comparable to or higher than those obtained using coordination anions of the PF 6 - , AsF 6 - and especially SbF 6 - type . The salts M + X - in which M is an alkali metal and X an anion identical to the anion of a compound of the present invention are known to be easily solvated in polymers, of which they slightly increase the glass transition temperature. In addition, the diffusion coefficient of the anion X - is higher than that of hexafluorometallate anions or tetrafluoroborate anions or phenylborate anions. These properties are explained by the delocalization of the negative charge and the flexibility of the anion around the SNS or SCS links.
Un autre avantage intéressant des composés polyioniques (A+X-)p de l'invention est l'absence d'éléments toxiques tels que P, As ou Sb, ces éléments étant par ailleurs considérés comme des agents contaminants dans les procédés de la micro-électronique.Another advantageous advantage of the polyionic compounds (A + X - ) p of the invention is the absence of toxic elements such as P, As or Sb, these elements being moreover considered as contaminating agents in the processes of micro -electronic.
Il faut en outre mentionner la possibilité de moduler les paramètres de solubilité et les températures de fusion des sels de l'invention par le choix des groupements RF, R' F ainsi que Q tels que définis ci-dessus, adaptés à la polarité du milieu d'utilisation pour les réactions de polymérisation, de réticulation ou d'amplification chimique. La très faible tension superficielle caractéristique des groupements perfluorés confère aux composés polyioniques (A+X-)p de l'invention des propriétés tensioactives utiles pour le mélange et le dispersion homogène de pigments et charges dans les mélanges polymérisables.It is also necessary to mention the possibility of modulating the solubility parameters and the melting temperatures of the salts of the invention by the choice of the groups R F , R ' F and also Q as defined above, adapted to the polarity of the medium of use for polymerization, crosslinking or chemical amplification reactions. The very low surface tension characteristic of perfluorinated groups gives the polyionic compounds (A + X - ) p of the invention surfactant properties useful for the mixing and the homogeneous dispersion of pigments and fillers in polymerizable mixtures.
La présente invention est décrite ci-après plus en détail, par les exemples suivants qui sont donnés à titre d'illustration, l'invention n'étant toutefois pas limitée à ces exemples.The present invention is described below in more detail, by the following examples which are given as illustrative, the invention however not being limited to these examples.
On a préparé un composé comprenant des groupements iodophényles en transformant les noyaux aromatiques d'un échantillon de polystyrène (Mw 6000) par iodation du polystyrène, oxydation en iodosoacétate par le mélange acide acétique / anhydride acétique / peroxyde d'hydrogène selon la méthode décrite par Yamada et al. (Die Makromolecular Chemie, (1972), 152, 153-162). 10 g du composé ainsi préparé ont été mis en suspension dans un mélange de 30 ml d'acide méthanesulfonique et 5 ml de butoxybenzène maintenu à 0°C pendant 4 heures. Le produit de réaction a été versé dans 400 ml d'un mélange 2:1 v/v éther : isopropanol et le précipité a été séparé par filtration, lavé par du THF et séché. 8 g du méthanesulfonate de polyiodonium ainsi obtenu ont été mis en suspension dans 50 ml d'eau et on a ajouté 10 g de sel de lithium du bis(nonafluorobutanesulfonyl)imidure de lithium en solution dans 25 ml d'eau. Le mélange a été agité pendant 1 heure et séparé par filtration. Le rendement de l'échange ionique (métathèse) est quantitatif pour l'obtention de bis(nonafluorobutanesulfonyl)imidure de poly(vinylphényl- (4-butoxyphényl)-4-iodonium. La structure du polymère est : A compound comprising iodophenyl groups was prepared by transforming the aromatic nuclei of a polystyrene sample (M w 6000) by iodization of the polystyrene, oxidation to iodosoacetate by the acetic acid / acetic anhydride / hydrogen peroxide mixture according to the method described. by Yamada et al. (Die Makromolecular Chemie, (1972), 152 , 153-162). 10 g of the compound thus prepared were suspended in a mixture of 30 ml of methanesulfonic acid and 5 ml of butoxybenzene maintained at 0 ° C for 4 hours. The reaction product was poured into 400 ml of a 2: 1 v / v ether: isopropanol mixture and the precipitate was separated by filtration, washed with THF and dried. 8 g of the polyiodonium methanesulfonate thus obtained were suspended in 50 ml of water and 10 g of lithium salt of bis (nonafluorobutanesulfonyl) imide lithium dissolved in 25 ml of water were added. The mixture was stirred for 1 hour and separated by filtration. The yield of ion exchange (metathesis) is quantitative for obtaining bis (nonafluorobutanesulfonyl) poly (vinylphenyl- (4-butoxyphenyl) -4-iodonium imide) imide. The structure of the polymer is:
3g du composé polyionique de l'exemple 1 ont été mélangés avec 5 ml de 4-butylphénylthioéther et 500 mg de benzoate de cuivre finement dispersés, et chauffés à 130° pendant trois heures en phase fondue. Après réaction, le mélange a été dissous dans 30 ml d'acétone et précipité dans 100 ml d'éther, à trois reprises, puis il a été traité dans le système acétone (solvant) / eau (précipitant).3 g of the polyionic compound of Example 1 were mixed with 5 ml of 4-butylphenylthioether and 500 mg of finely dispersed copper benzoate, heated to 130 ° for three hours in the melt phase. After reaction, the mixture was dissolved in 30 ml of acetone and precipitated in 100 ml of ether three times and then it was treated in the acetone (solvent) / water system (precipitating).
On a obtenu le sel de polysulfonium : The polysulfonium salt was obtained:
Les paramètres de solubilité des deux composés polymères ioniques obtenus dans les exemples 1 et 2 sont résumés dans le tableau suivant : The solubility parameters of the two ionic polymer compounds obtained in Examples 1 and 2 are summarized in the following table:
Le caractère exceptionnel de solubilité de polyélectrolytes possédant une densité de charge élevée est ainsi mis en évidence.The exceptional solubility of polyelectrolytes with a high charge density is thus highlighted.
On a préparé un polymère similaire à celui de l'exemple 1 mais avec un groupement méthoxy au lieu de butoxy, par action du poly(4-iodostyrène) (23 g) sur l'anisole (10,8 g) en présence d'acide peracétique (45,6 g) et d'acide toluènesulfonique (19,05 g) dans le dichlorométhane (40 ml) en suivant le mode opératoire de Crivello & Lee, (US. 4,780,511). On a dispersé 25 g du polymère obtenu dans un mélange 1:1 d'éthanol et d'acétone, auquel on a ajouté 15 g de sel de sodium de la bis (trifuorométhanesulfonyl)imide. La solution visqueuse obtenue a été centrifugée pour éliminer le toluènesulfonate de sodium, puis précipitée par l'eau. On a ainsi obtenu une poudre jaune soluble dans les solvants usuels.A polymer similar to that of example 1 but with a methoxy group instead of butoxy, by the action of poly (4-iodostyrene) (23 g) on anisole (10.8 g) in the presence of peracetic acid (45.6 g) and toluenesulfonic acid (19.05 g) in the dichloromethane (40 ml) following the procedure for Crivello & Lee, (US 4,780,511). 25 g of the polymer obtained in a 1: 1 mixture of ethanol and acetone, to which 15 g of sodium salt from the bis (trifuoromethanesulfonyl) imide. The viscous solution obtained was centrifuged to remove toluenesulfonate sodium, then precipitated by water. We thus obtained a yellow powder soluble in the usual solvents.
On a préparé le phénoxyéthylvinyléther en faisant réagir le chloroéthylvinyléther sur le phénate de sodium, puis on a effectué une polymérisation dans le dichlorométhane initiée par TiCl4 à -10°C. Par réaction de 8,2 g du polymère ainsi obtenu sur 9,8 g de phényliodosotoluène sulfonate dans 40 ml d'un mélange équivolumique d'acide acétique et de dichlorométhane, on a obtenu un polyiodonium qui a été précipité par l'éther. La réaction d'échange ionique a ensuite été conduite de la même manière que dans l'exemple 3 entre 12 g de polymère et 7 g de sel de sodium de la bis(trifluorométhanesulfonyl)imide. Après précipitation et lavage à l'eau, on a obtenu une masse collante qui peut être utilisée en solution à 50% dans la méthyléthylcétone.The phenoxyethylvinyl ether was prepared by reacting the chloroethylvinyl ether with the sodium phenate, then polymerization in dichloromethane initiated by TiCl 4 was carried out at -10 ° C. By reacting 8.2 g of the polymer thus obtained with 9.8 g of phenyliodosotoluene sulfonate in 40 ml of an equivolumic mixture of acetic acid and dichloromethane, a polyiodonium was obtained which was precipitated with ether. The ion exchange reaction was then carried out in the same manner as in Example 3 between 12 g of polymer and 7 g of sodium salt of the bis (trifluoromethanesulfonyl) imide. After precipitation and washing with water, a sticky mass was obtained which can be used in 50% solution in methyl ethyl ketone.
Un oligomère contenant des groupements iodonium a été préparé selon la méthode décrite dans J. Polym. Sci., Polym. Lett. (1976), 14, 65 sous forme de bromure, par action de 5,7 g de 1,4-bis(diacétoxyiodo)phénylène sur 20 ml de 1,3-diphénylpropane dans 300 ml d'anhydride acétique et 40 ml d'acide sulfurique à 0°C. Le mélange a été versé dans 1 l d'eau contenant 80 g de bromure de sodium et 100 g d'acétate de sodium. Le précipité a été filtré, lavé à l'éther et séché. 4 g de cet oligomère ont été mis en solution dans 50 ml d'eau et on a ajouté 5 g de tris(trifluorométhanesulfonyl)méthylure de sodium dissous dans 25 ml d'eau. Le tris(trifluorométhanesulfonyl)méthylure de polyiodonium a précipité et a été séparé par filtration. Il est soluble dans les solvants polaires usuels comme l'acétone, ou dans des monomères comme le (4-propényloxymethylène)-1,3dioxolane-2one (PEPC commercialisé par International Specialty Products, Wayne, NJ, USA) . Il faut noter qu'un bromure d'un cation polyiodonium identique ne possède qu'une solubilité négligeable dans les solvants les plus polaires connus, tels que le diméthylsulfoxyde (DMSO), le diméthylformamide (DMF), ou l'hexaméthylphosphoramide (HMPA).An oligomer containing iodonium groups was prepared according to the method described in J. Polym. Sci., Polym. Lett. (1976), 14 , 65 in the form of bromide, by the action of 5.7 g of 1,4-bis (diacetoxyiodo) phenylene on 20 ml of 1,3-diphenylpropane in 300 ml of acetic anhydride and 40 ml of sulfuric acid at 0 ° C. The mixture was poured into 1 l of water containing 80 g of sodium bromide and 100 g of sodium acetate. The precipitate was filtered, washed with ether and dried. 4 g of this oligomer were dissolved in 50 ml of water and 5 g of sodium tris (trifluoromethanesulfonyl) methylide dissolved in 25 ml of water were added. The polyiodonium tris (trifluoromethanesulfonyl) methylide precipitated and was separated by filtration. It is soluble in the usual polar solvents such as acetone, or in monomers such as (4-propenyloxymethylene) -1,3dioxolane-2one (PEPC marketed by International Specialty Products, Wayne, NJ, USA). It should be noted that a bromide of an identical polyiodonium cation has only negligible solubility in the most polar solvents known, such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), or hexamethylphosphoramide (HMPA).
Les propriétés de solubilité de certains composés polyioniques de la présente invention ont été comparées aux propriétés d'un poly(iodonium) préparé selon Crivello & Lam (J. Polym. Sci.; Polymer Chemistry, (1979), 17, 3845-3858). Le polyiodonium selon Crivello et al a été obtenu par une trans-addition du chlorure de (4,4'-N-maléimido)diphényliodonium avec le 1,10-décanethiol dans le m-crésol en présence d'une base tertiaire, suivie d'une métathèse en présence de NaPF6. Les composés de la présente invention ont été préparés de la même manière, mais en remplaçant pour la métathèse NaPF6 par l'un des sels suivants : Na+ (CF3SO2)2N-, Na+ (CF3SO2)N(SO2C4F9)-, Na+(CF3SO2)3C-.The solubility properties of certain polyionic compounds of the present invention were compared with the properties of a poly (iodonium) prepared according to Crivello & Lam (J. Polym. Sci .; Polymer Chemistry, (1979), 17 , 3845-3858) . The polyiodonium according to Crivello et al was obtained by a trans-addition of (4,4'-N-maleimido) diphenyliodonium chloride with 1,10-decanethiol in m-cresol in the presence of a tertiary base, followed by '' a metathesis in the presence of NaPF 6 . The compounds of the present invention were prepared in the same way, but replacing for metathesis NaPF 6 with one of the following salts: Na + (CF 3 SO 2 ) 2 N - , Na + (CF 3 SO 2 ) N (SO 2 C 4 F 9 ) - , Na + (CF 3 SO 2 ) 3 C - .
Les résultats sont groupés dans le tableau suivant : The results are grouped in the following table:
Un polythioéther a été préparé par réaction de 15 g de dimercaptohexane avec 18,67 g de 1,2 bis(2-chloroéthoxy) éthane dans 200 ml de N-méthylpyrrolidone à 150°C en présence de 10 g de carbonate de potassium. Le polymère obtenu a été précipité dans l'eau et purifié par plusieurs opérations de dissolution (CH2Cl2) / précipitation (diéthyléther), puis séparé par centrifugation dans un récipient unique. Le polymère se présente sous la forme d'une masse collante.A polythioether was prepared by reacting 15 g of dimercaptohexane with 18.67 g of 1.2 bis (2-chloroethoxy) ethane in 200 ml of N-methylpyrrolidone at 150 ° C in the presence of 10 g of potassium carbonate. The polymer obtained was precipitated in water and purified by several dissolution (CH 2 Cl 2 ) / precipitation (diethyl ether) operations, then separated by centrifugation in a single container. The polymer is in the form of a sticky mass.
On a ensuite introduit 7g du polymère dissous dans 120 ml de dichlorométhane (CH2Cl2) dans un ballon tricol équipé d'un réfrigérant, d'une agitation mécanique et d'une entrée de gaz neutre (argon), et on a ajouté goutte à goutte 4,8 g de 2-bromoacétophénone. Le mélange a été chauffé au reflux 40°C. Un précipité est apparu rapidement. La réaction a été poursuivie 12 heures après l'apparition du précipité. Le bromure de polyphénacylsulfonium a été séparé par filtration et lavé avec du dichlorométhane et de l'éther. 5 g du composé polyionique ont été dissous dans 60 ml d'eau, la solution a été filtrée, puis on a ajouté sous agitation 3 g de sel de lithium de bis(trifluorométhanesulfonyl)imide (Li[CF3SO2]2N) en solution dans 25 ml d'eau. Un précipité s'est formé immédiatement et l'agitation a été poursuivie pendant 1 h. Le polymère a été séparé par filtration et séché. Le polymère a été obtenu avec un rendement quantitatif.Then 7 g of the polymer dissolved in 120 ml of dichloromethane (CH 2 Cl 2 ) were introduced into a three-necked flask equipped with a condenser, mechanical stirring and an inlet for neutral gas (argon), and added 4.8 g of 2-bromoacetophenone drop by drop. The mixture was heated to reflux 40 ° C. A precipitate appeared quickly. The reaction was continued 12 hours after the appearance of the precipitate. The polyphenacylsulfonium bromide was separated by filtration and washed with dichloromethane and ether. 5 g of the polyionic compound were dissolved in 60 ml of water, the solution was filtered, then 3 g of lithium salt of bis (trifluoromethanesulfonyl) imide (Li [CF 3 SO 2 ] 2 N) was added with stirring in solution in 25 ml of water. A precipitate formed immediately and the stirring was continued for 1 h. The polymer was separated by filtration and dried. The polymer was obtained in quantitative yield.
Les propriétés de solubilité du composé polyionique obtenu sont résumées dans le tableau suivant: The solubility properties of the polyionic compound obtained are summarized in the following table:
Un polythioéther similaire à celui de l'exemple précédent a été préparé par réaction de 8 g de 2-mercaptoéthyléther avec 15,3 g de a,a-dibromo-m-xylène dans 100 ml de diméthylformamide à 80°C en présence de 4 g de carbonate de potassium. Le polymère a été précipité dans l'eau et purifié comme précédemment. Dans un ballon tricol équipé d'un réfrigérant, d'une agitation mécanique et d'une entrée de gaz neutre (Argon), 10 g du polymère ont été dissous dans 120 ml d'hexane et on a ajouté goutte à goutte 11,5 g de bromoacétyl-4-octyloxybenzène). Le mélange a été chauffé au reflux à 60°C. Un précipité est apparu rapidement. La réaction a été poursuivie 12 heures après l'apparition du précipité. Le bromure de polyphénacylsulfonium a été séparé par filtration et lavé avec de l'hexane et de l'éther. 7 g du composé polyionique ont été mis en suspension dans 60 ml d'acétone et 5,15 g de sel de potassium du tris(trifluorométhanesulfonyl)méthane (K[CF3SO2]3C) ont été ajoutés sous agitation. Le mélange réactionnel a été maintenu sous agitation pendant 1 heure à température ambiante, puis la solution a été filtrée pour éliminer le bromure de potassium formé. L'acétone a été évaporée et on a obtenu une masse très visqueuse du composé polyionique. A polythioether similar to that of the previous example was prepared by reacting 8 g of 2-mercaptoethyl ether with 15.3 g of a, a-dibromo-m-xylene in 100 ml of dimethylformamide at 80 ° C in the presence of 4 g of potassium carbonate. The polymer was precipitated in water and purified as before. In a three-necked flask equipped with a condenser, mechanical stirring and a neutral gas inlet (Argon), 10 g of the polymer were dissolved in 120 ml of hexane and 11.5 was added dropwise g of bromoacetyl-4-octyloxybenzene). The mixture was heated to reflux at 60 ° C. A precipitate appeared quickly. The reaction was continued 12 hours after the appearance of the precipitate. The polyphenacylsulfonium bromide was separated by filtration and washed with hexane and ether. 7 g of the polyionic compound were suspended in 60 ml of acetone and 5.15 g of potassium salt of tris (trifluoromethanesulfonyl) methane (K [CF 3 SO 2 ] 3 C) were added with stirring. The reaction mixture was stirred for 1 hour at room temperature, then the solution was filtered to remove the potassium bromide formed. The acetone was evaporated and a very viscous mass of the polyionic compound was obtained.
Les propriétés de solubilité du composé polyionique
obtenu sont indiquées dans le tableau suivant :
Mw Å 1250
M w Å 1250
6,5 g de trifluorométhanesulfonamide CF3SO2NH2 et 10,8 ml de pyridine dans 60 ml de dichlorométhane ont été refroidis à -15°C et on a ajouté goutte à goutte 3,6 ml de chlorure de sulfuryle dans 10 ml de dichlorométhane, puis 4,6 ml de 1,1,1,3,3,3-hexafluoro-2-propanol. Le mélange a été agité pendant 1 heure à -15°C, puis 4 heures à température ambiante (25°C). Le mélange réactionnel a ensuite été filtré et le solvant a été éliminé à l'aide d'un évaporateur rotatif. Le résidu solide obtenu a été dissous dans 50 ml d'eau contenant 5 g d'acétate de sodium, et 18,45 g de bis(hexafluorophosphate de bis[4-(diphénylsulfonio)phényl]thioéther préparé selon la méthode d'Akhtar et al. (Chem. Mat. (1990), 2, 732 et K.T. Chang, US 4,197,174) et finement pulvérisé ont été ajoutés. Le mélange a été introduit dans un flacon de polyéthylène rigide contenant des boulets d'oxyde de zirconium et agité à la température de la pièce pendant 3 h dans un broyeur à rouleaux. La suspension obtenue a été filtrée et le solide obtenu a été séché. On a ainsi obtenu 28 g (rendement = 78%) du composé de structure suivante : 6.5 g of trifluoromethanesulfonamide CF 3 SO 2 NH 2 and 10.8 ml of pyridine in 60 ml of dichloromethane were cooled to -15 ° C and 3.6 ml of sulfuryl chloride in 10 ml were added dropwise of dichloromethane, then 4.6 ml of 1,1,1,3,3,3-hexafluoro-2-propanol. The mixture was stirred for 1 hour at -15 ° C, then 4 hours at room temperature (25 ° C). The reaction mixture was then filtered and the solvent was removed using a rotary evaporator. The solid residue obtained was dissolved in 50 ml of water containing 5 g of sodium acetate, and 18.45 g of bis (bis [4- (diphenylsulfonio) phenyl] phenyl] thioether bis (hexafluorophosphate) prepared according to the method of Akhtar and al. (Chem. Mat. (1990), 2 , 732 and KT Chang, US 4,197,174) and finely pulverized were added The mixture was introduced into a rigid polyethylene bottle containing zirconium oxide balls and stirred at the temperature of the part for 3 h in a roller mill. The suspension obtained was filtered and the solid obtained was dried. 28 g (yield = 78%) of the compound with the following structure were thus obtained:
A 4 g de dimère cyclopentadiényl-fer-dicarbonyle (commercialisé par Aldrich, Milwaukee, USA) dissous dans 20 ml d'acétonitrile et maintenu à 0°C, on a ajouté (en maintenant une forte agitation) 0,58 ml de brome dilué dans 5 ml d'acétonitrile ; la réaction de formation du sel CpFe(CO)2Br a été immédiate et quantitative. 20 g de 2isopropényl-4-cumène (p-isopropyl-styrène) ont été polymérisés dans 200 ml de dichlorométhane à -10°C par amorçage cationique initié par 150 µl de SnCl4. Le polymère a été précipité dans l'éther et purifié par plusieurs opérations de dissolution (CH2Cl2) / précipitation (diéthyléther). On a obtenu le polymère sous forme d'un solide blanc, avec un rendement de 63%. Dans un ballon tricol équipé d'un réfrigérant, d'une agitation mécanique et d'une entrée de gaz neutre (Argon), 8,2 g du polymère ont été dissous dans 120 ml de dichloroéthane (C2H4Cl2) et on a ajouté la solution de CpFe(CO)2Br dans l'acétonitrile préparée précédemment. Le mélange a été chauffé au reflux. Un précipité s'est formé avec dégagement concomitant de monoxyde de carbone. La réaction a été poursuivie 2 heures après l'apparition du précipité. Le bromure de poly(arèneferrocènium) a été séparé par filtration et lavé avec du dichlorométhane et de l'acétonitrile. 3 g du composé polyionique ont été dissous dans 50 ml d'eau auxquels ont été ajoutés 3,8 g de sel de lithium de (nonafluorobutanesulfonyl)-(trifluorométhylsulfonyl)imide (Li[C4F9SO2NSO2CF3]) dans 25 ml d'eau ; un précipité s'est formé immédiatement et l'agitation a été poursuivie pendant 1 h. Le polymère a été séparé par filtration et séché. Il a été obtenu avec un rendement quantitatif.To 4 g of cyclopentadienyl-iron-dicarbonyl dimer (marketed by Aldrich, Milwaukee, USA) dissolved in 20 ml of acetonitrile and maintained at 0 ° C., 0.58 ml of diluted bromine was added (maintaining vigorous stirring) in 5 ml of acetonitrile; the salt formation reaction CpFe (CO) 2Br was immediate and quantitative. 20 g of 2isopropenyl-4-cumene (p-isopropyl-styrene) were polymerized in 200 ml of dichloromethane at -10 ° C by cationic initiation initiated with 150 μl of SnCl 4 . The polymer was precipitated in ether and purified by several dissolution (CH 2 Cl 2 ) / precipitation (diethyl ether) operations. The polymer was obtained in the form of a white solid, with a yield of 63%. In a three-necked flask equipped with a condenser, mechanical stirring and a neutral gas inlet (Argon), 8.2 g of the polymer were dissolved in 120 ml of dichloroethane (C 2 H 4 Cl 2 ) and the solution of CpFe (CO) 2 Br in acetonitrile previously prepared was added. The mixture was heated to reflux. A precipitate formed with concomitant evolution of carbon monoxide. The reaction was continued 2 hours after the appearance of the precipitate. The poly (areneferrocenium) bromide was separated by filtration and washed with dichloromethane and acetonitrile. 3 g of the polyionic compound were dissolved in 50 ml of water to which were added 3.8 g of lithium salt of (nonafluorobutanesulfonyl) - (trifluoromethylsulfonyl) imide (Li [C 4 F 9 SO 2 NSO 2 CF 3 ]) in 25 ml of water; a precipitate formed immediately and the stirring was continued for 1 h. The polymer was separated by filtration and dried. It was obtained with a quantitative yield.
Un autre composé polyionique a été préparé de la même manière, mais en remplaçant le sel de lithium de (nonafluorobutanesulfonyl)-(trifluorométhylsulfonyl)-imide par 1,5 g d'hexafluorophosphate de sodium. Les propriétés de solubilité des deux composés polyioniques obtenus sont résumées à titre indicatif dans le tableau suivant: Another polyionic compound was prepared in the same way, but replacing the lithium salt of (nonafluorobutanesulfonyl) - (trifluoromethylsulfonyl) -imide with 1.5 g of sodium hexafluorophosphate. The solubility properties of the two polyionic compounds obtained are summarized by way of indication in the following table:
A 5 g de 1,2-diferrocenyléthane (commercialisé par Aldrich C°, Milwaukee, USA) en solution dans 50 ml de toluène on a ajouté 3,4 g de [bis(trifluoroacétoxy)iodo]benzène. Un précipité bleu qui s'est formé immédiatement, a été séparé, lavé à l'éther et séché. 5 g de ce solide ont été mis en solution dans 25 ml d'eau et on y a ajouté 4,9 g de bis(trifluorométhanesulfonyl)imidure de sodium. On a obtenu une précipité de sel de l'anion imidure du dimère du ferrocène sous forme d'une poudre cristalline bleue, avec un rendement quantitatif. 5 g of 1,2-diferrocenylethane (marketed by Aldrich C °, Milwaukee, USA) in solution in 50 ml of toluene was added 3.4 g of [bis (trifluoroacetoxy) iodo] benzene. A blue precipitate that has formed immediately was separated, washed with ether and dried. 5 g of this solid were dissolved in 25 ml of water and added 4.9 g of bis (trifluoromethanesulfonyl) imide sodium. A salt precipitate of the imide anion was obtained of ferrocene dimer in the form of a crystalline powder blue, with a quantitative yield.
On a ajouté 3,3 g de [bis(trifluoroacétoxy)-iodo]benzène (commercialisé par Aldrich) à 6 g d'un copolymère de vinylferrocène (commercialisé par Aldrich C°, Milwaukee, USA) et de méthacrylate de butyle contenant 42% de motifs organométalliques obtenu par polymérisation radicalaire induite par l'azobis(butyronitrile) en solution dans le toluène). Un précipité bleu s'est formé immédiatement et il a été séparé, puis lavé à l'éther pour éliminer l'excès d'oxydant, et séché. 5g de ce composé polyionique (dans lequel le polycation de ferricinium est associé à l'anion trifluoroacétate) ont été mis en suspension dans 25 ml d'eau à laquelle ont été ajoutés 3 g de bis(trifluorométhanesulfonyl)imidure de sodium. Le précipité du composé polyionique de l'anion imidure du polyferricinium a été obtenu avec un rendement quantitatif sous forme d'une poudre amorphe bleue soluble dans la plupart des solvants usuels.3.3 g of [bis (trifluoroacetoxy) -iodo] benzene was added (marketed by Aldrich) at 6 g of a vinylferrocene copolymer (marketed by Aldrich C °, Milwaukee, USA) and butyl methacrylate containing 42% of organometallic units obtained by polymerization radical induced by azobis (butyronitrile) in solution in toluene). A blue precipitate has formed immediately and it was separated and then washed with ether to remove excess oxidant, and dried. 5g of this compound polyionic (in which the ferricinium polycation is associated with the trifluoroacetate anion) have been suspension in 25 ml of water to which 3 g have been added of sodium bis (trifluoromethanesulfonyl) imide. The precipitate of the polyionic compound of the imide anion of polyferricinium was obtained with a quantitative yield in the form of a blue amorphous powder soluble in the most common solvents.
Dans un ballon tricol équipé d'un réfrigérant, d'une agitation mécanique et d'une entrée de gaz neutre (Argon), 9,5 g d'un copolymère de diméthylsiloxane et d'(hydrogéno) (méthyl)-siloxane (HMS 301 25% SiH, Mw 1900, commercialisé par Gelest Inc., Tullytown, PA, USA) ont été mis en solution dans le THF. On a ajouté 7,9 g d'allylferrocène et 70 mg d'acide chloroplatinique H2PtCl6. Le mélange a été chauffé au reflux pendant 4 heures. Un prélèvement a permis de confirmer la disparition complète des bandes IR de la liaison SiH. Le polymère a été précipité dans le méthanol et purifié par trois opérations de dissolution (THF) / précipitation (méthanol). A 5,4 g de ce polymère en solution dans le dichlorométhane, on a ajouté 2,4 g de [bis(trifluoroacétoxy)iodo]benzène. Le produit de réaction a été versé dans 100 ml d'éther et le précipité a été séparé par centrifugation. Une métathèse permettant de remplacer l'anion trifluoroacétate par l'anion tris(trifluorométhanesulfonyl) méthylure a été effectuée dans l'eau (100 ml) entre 4,2 g du poly(cation) et 3,1 g du sel de sodium tris(trifluorométhanesulfonyl)méthylure de sodium dissous dans 25 ml d'eau. Le polymère a été séparé par centrifugation et se présente sous le forme d'une masse gommeuse bleue soluble dans la plupart de solvant, y compris à des teneurs > 3% dans les huiles siliconées. La structure du polymère est la suivante : 9.5 g of a dimethylsiloxane and (hydrogen) (methyl) -siloxane (HMS) copolymer in a three-necked flask equipped with a condenser, mechanical stirring and a neutral gas inlet (Argon) 301 25% SiH, M w 1900, marketed by Gelest Inc., Tullytown, PA, USA) were dissolved in THF. 7.9 g of allylferrocene and 70 mg of chloroplatinic acid H 2 PtCl 6 were added . The mixture was heated at reflux for 4 hours. A sample confirmed the complete disappearance of the IR bands from the SiH bond. The polymer was precipitated in methanol and purified by three dissolution (THF) / precipitation (methanol) operations. To 5.4 g of this polymer in solution in dichloromethane, 2.4 g of [bis (trifluoroacetoxy) iodo] benzene were added. The reaction product was poured into 100 ml of ether and the precipitate was separated by centrifugation. A metathesis allowing the trifluoroacetate anion to be replaced by the tris (trifluoromethanesulfonyl) methylide anion was carried out in water (100 ml) between 4.2 g of the poly (cation) and 3.1 g of the sodium salt tris ( trifluoromethanesulfonyl) sodium methylide dissolved in 25 ml of water. The polymer has been separated by centrifugation and is in the form of a blue gummy mass soluble in most solvents, including at contents> 3% in silicone oils. The structure of the polymer is as follows:
Un oligomère de diazonium a été préparé selon la méthode décrite dans U.S. 2,714,066 par condensation du chlorozincate de 4-diazodiphénylamine avec la formaldéhyde. 25 g de ce composé polyionique ont été dissous dans 500 ml d'eau maintenue à 0°C et contenant 50 g d'acétate de sodium et 28 g de di-sel de sodium de l'acide éthylène diamine tétraacétique (EDTA). On a ajouté alors 24 g de sel de sodium de la bis(trifluorométhanesulfonyl)imide en solution dans 50 ml d'eau. Le composé polyionique a été séparé par filtration et séché (rendement quantitatif), et conservé à 0°C à l'abri de la lumière. Ce composé est très soluble dans les solvants organiques usuels moyennement polaires tels que la MEK, et soluble dans les monomères de type DVE-3 ou PEPC, ou les éthers glycidiques.A diazonium oligomer was prepared according to the method described in U.S. 2,714,066 by condensation of 4-diazodiphenylamine chlorozincate with formaldehyde. 25 g of this polyionic compound were dissolved in 500 ml water kept at 0 ° C and containing 50 g of sodium acetate and 28 g of sodium di-salt of ethylene diamine acid tetraacetic (EDTA). 24 g of salt were then added. bis (trifluoromethanesulfonyl) imide sodium solution in 50 ml of water. The polyionic compound has been separated by filtration and dried (quantitative yield), and stored at 0 ° C protected from light. This compound is very slightly soluble in usual organic solvents polar such as MEK, and soluble in the monomers of type DVE-3 or PEPC, or glycidic ethers.
A 2 g de poly(4-hydroxystyrène)-co-styrène (8:2) (commercialisé par Shinetsu, Japon) en solution dans 20 ml de diméthylformamide, ont été ajoutés 9,7 ml d'une solution 1M d'hydroxyde de potassium dans le méthanol et 1,3 g de chloroéthylvinyléther. La solution a été chauffée à 80°C pendant 1 heure et le mélange réactionnel a été versé dans 100 ml d'eau, où le poly(4-vinyloxyéthyl)-styrène formé a précipité. Le polymère a été purifié par plusieurs opérations de dissolution / précipitation dans l'acétone (solvant) / eau (précipitant) et acétone (solvant) / éther (précipitant). 1 g de poly(4-vinyloxyéthyl)-styrène-co-styrène et 20 mg du polymère de l'exemple 1 dans 10 ml de MEK ont été déposés à la tournette (spin-coated) sur un substrat de silicium de manière à former un film de 0,5 µm d'épaisseur. Le film a été soumis à une exposition de 1 MJ/cm2 obtenue par un laser KrF à travers un masque interférentiel. Le développement a été effectué par le THF. La résolution obtenue, observée par microscope électronique (SEM), est de l'ordre de l'épaisseur du film, soit 0,5 µm. Ce photorésist ne contient aucun élément métallique susceptible de contaminer le silicium.To 2 g of poly (4-hydroxystyrene) -co-styrene (8: 2) (marketed by Shinetsu, Japan) dissolved in 20 ml of dimethylformamide, were added 9.7 ml of a 1M hydroxide solution potassium in methanol and 1.3 g of chloroethylvinyl ether. The solution was heated at 80 ° C for 1 hour and the reaction mixture was poured into 100 ml of water, where the poly (4-vinyloxyethyl) -styrene formed precipitated. The polymer was purified by several dissolution / precipitation operations in acetone (solvent) / water (precipitant) and acetone (solvent) / ether (precipitant). 1 g of poly (4-vinyloxyethyl) -styrene-co-styrene and 20 mg of the polymer of Example 1 in 10 ml of MEK were deposited with a spin-coating on a silicon substrate so as to form a 0.5 µm thick film. The film was subjected to an exposure of 1 MJ / cm 2 obtained by a KrF laser through an interference mask. Development was carried out by THF. The resolution obtained, observed by electron microscope (SEM), is of the order of the film thickness, ie 0.5 μm. This photoresist does not contain any metallic element likely to contaminate the silicon.
1g de poly(4-t-butoxycarboxystyrène) dans le dichloroéthane et 60 mg du polymère de l'exemple 8 ont été déposés à la tournette (spin-coated) sur un substrat de silicium de manière à former un film de 0,5 µm d'épaisseur. Le film a ensuite été soumis à une exposition de 1 MJ/cm2 obtenue par un laser KrF à travers un masque interférentiel. Le développement a été effectué par une solution à 4% d'hydroxyde de tétraméthyl ammonium dans l'eau. La résolution obtenue, observée par microscope électronique (SEM), est de l'ordre de l'épaisseur du film, soit 0,5 µm. Ce photorésist ne contient aucun élément métallique susceptible de contaminer le silicium.1g of poly (4-t-butoxycarboxystyrene) in dichloroethane and 60 mg of the polymer of Example 8 were deposited with the spin spin (coated) on a silicon substrate so as to form a film of 0.5 μm thick. The film was then subjected to an exposure of 1 MJ / cm 2 obtained by a KrF laser through an interference mask. Development was carried out with a 4% solution of tetramethyl ammonium hydroxide in water. The resolution obtained, observed by electron microscope (SEM), is of the order of the film thickness, ie 0.5 μm. This photoresist does not contain any metallic element likely to contaminate the silicon.
Les propriétés de photo-amorçage des composés polyioniques de l'invention sont illustrées sur le tableau suivant.The photo-priming properties of the compounds polyionics of the invention are illustrated in the table following.
Les composés polyioniques des exemples précédents ont été utilisés à raison de 1% en poids dans différents monomères et irradiés par un rayonnement U.V. à 254 nm avec une puissance de 1900 mW/cm2 durant une durée de 5 secondes, suivie d'une période de 10 minutes permettant la propagation des espèces générées dans le milieu (postcure). Les résultats sont indiqués dans le tableau ci-après. The polyionic compounds of the previous examples were used in an amount of 1% by weight in different monomers and irradiated by UV radiation at 254 nm with a power of 1900 mW / cm 2 for a period of 5 seconds, followed by a period of 10 minutes allowing the propagation of the species generated in the environment (aftercare). The results are shown in the table below.
Claims (23)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2187046 | 1996-10-03 | ||
CA002187046A CA2187046A1 (en) | 1996-10-03 | 1996-10-03 | Sulfonylimides and sulfonylmethylides, use thereof as photoinitiators |
Publications (3)
Publication Number | Publication Date |
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EP0834502A2 true EP0834502A2 (en) | 1998-04-08 |
EP0834502A3 EP0834502A3 (en) | 2003-10-08 |
EP0834502B1 EP0834502B1 (en) | 2005-12-28 |
Family
ID=4159016
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402311A Expired - Lifetime EP0834502B1 (en) | 1996-10-03 | 1997-10-02 | Polymeric polyionic compounds, process for their preparation and their use as photoinitiators |
EP97402312A Expired - Lifetime EP0834492B1 (en) | 1996-10-03 | 1997-10-02 | Fluorinated ionic sulphonylimides and sulphonylmethylides, process for their preparation and their use as photoinitiators |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402312A Expired - Lifetime EP0834492B1 (en) | 1996-10-03 | 1997-10-02 | Fluorinated ionic sulphonylimides and sulphonylmethylides, process for their preparation and their use as photoinitiators |
Country Status (5)
Country | Link |
---|---|
US (2) | US6008267A (en) |
EP (2) | EP0834502B1 (en) |
JP (2) | JP4226672B2 (en) |
CA (1) | CA2187046A1 (en) |
DE (2) | DE69734958T2 (en) |
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Also Published As
Publication number | Publication date |
---|---|
US6008265A (en) | 1999-12-28 |
EP0834492B1 (en) | 2005-12-28 |
DE69734959D1 (en) | 2006-02-02 |
EP0834502B1 (en) | 2005-12-28 |
EP0834492A2 (en) | 1998-04-08 |
JP4226672B2 (en) | 2009-02-18 |
DE69734958D1 (en) | 2006-02-02 |
JPH10226707A (en) | 1998-08-25 |
DE69734959T2 (en) | 2006-08-10 |
DE69734958T2 (en) | 2006-08-10 |
US6008267A (en) | 1999-12-28 |
EP0834502A3 (en) | 2003-10-08 |
CA2187046A1 (en) | 1998-04-03 |
JPH10226658A (en) | 1998-08-25 |
EP0834492A3 (en) | 2003-10-08 |
JP3988963B2 (en) | 2007-10-10 |
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